TW202340290A - Polymer, polymer solution, photosensitive resin composition and cured product - Google Patents

Abstract

A polymer including a structural unit represented by formula (NB), a structural unit represented by formula (AD), and at least one structural unit selected from among structural units represented by formula (1-2) and structural units represented by formula (1-3). In formula (NB), R1, R2, R3, and R4 are each independently a hydrogen atom or a C1-C30 organic group, a1 is 0, 1, or 2, and R13 and R14 are each independently a hydrogen atom or a C1-C3 alkyl group. In formula (AD), R11 and R12 are each independently a C1-C12, linear or branched alkyl group. In formula (1-2), Rp is a group having two or more (meth)acryloyl groups and R22 is a hydrogen atom or a C1-C3 organic group. In formula (1-3), Rs is a group having one (meth)acryloyl group and R22 is a hydrogen atom or a C1-C3 organic group.

Description

Polymers, polymer solutions, photosensitive resin compositions and hardened products

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.

A liquid crystal display device or a solid-state imaging element usually includes a color filter or a black matrix, a spacer (for example, a photospacer, a colored spacer, a black spacer), and a partition material (for example, a transparent bank or a black bank). The color filter, the black matrix, the spacer, and the partition material are composed of structures such as colored patterns or protective films formed on the substrate. As a method of forming colored patterns or protective films in these structures, photolithography using a photosensitive resin composition has become a mainstream method. Various studies have been conducted on photosensitive resin compositions. For example, Patent Document 1 describes a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. The alkali-soluble resin It contains a group having an acidic group and two or more mutually different polymerizable unsaturated groups at least in the side chain. Moreover, the Example of Patent Document 1 describes that a methacrylic acid/allyl methacrylate/epoxypropyl adduct is synthesized as an alkali-soluble resin and is used to prepare a photosensitive resin composition. [Prior technical literature] [Patent Document]

[Patent Document 1] International Publication No. 2012/147706

[Problem to be solved by the invention]

The photosensitive resin composition used to form a color filter, a black matrix, a spacer, or a partition material uses a resin that has the property of being hardened by a polymerization reaction caused by light. Color filters, black matrices, spacers, or partition materials are produced by patterning a photosensitive resin composition by exposure and development and then hardening the composition. In photosensitive resin compositions, "higher sensitivity" is also considered to be a common issue, but as display devices and imaging devices become more complex or more popular, higher levels of high sensitivity are required. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, thereby improving productivity. In addition, the photosensitive resin composition is required to have excellent processability during development using an alkaline developer. In addition, the cured product of the photosensitive resin composition is required to have high transparency. Furthermore, especially when the photosensitive resin composition contains dyes and pigments, during exposure, it is difficult for light to reach the bottom surface of the pattern compared to the upper surface of the pattern, and the curing by exposure becomes insufficient, which may result in problems during development. This causes the bottom side of the pattern to dissolve. In this case, when the pattern is melted by heat during curing after development, the melted portion on the bottom side of the pattern can be filled. Therefore, the cured product of the photosensitive resin composition is required to have a low softening point or melting point. [Technical means to solve the problem]

The inventors of the present invention have found that by improving the polymer used in the photosensitive resin composition or blending the composition, it is possible to obtain a photosensitive resin composition having a low softening point and melting point, thereby improving processability or pattern formation in photolithography processing. The present invention was completed by creating a resin cured product that is excellent and has sensitivity, alkali solubility, and heat yellowing resistance in a good balance.

According to the present invention, a polymer, a polymer solution, a photosensitive resin composition, and a cured product shown below can be provided. [1] A polymer containing: a structural unit represented by formula (NB); a structural unit represented by formula (AD); and a structural unit selected from the group consisting of formula (1-2) and formula (1-3) ) at least 1 structural unit among the structural units represented by , wherein, In the general formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2, In the formula (AD), R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. , In formula (1-2), R ^p is a group having two or more (meth)acrylyl groups, R ²² is a hydrogen atom or an organic group having 1 to 3 carbon atoms, In formula (1-3), R ^s is a group having one (meth)acrylyl group, and R ²² is a hydrogen atom or an organic group having 1 to 3 carbon atoms. [2] The polymer of item [1], which further contains a structural unit represented by formula (1-1), In the formula (1-1), R ²¹ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, Z is a group containing one or more (meth)acrylyl groups, Q is a hydrogen atom or a substituted or unsubstituted group. Substituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. When Q is the aforementioned alkyl group and X is the aforementioned alkylene group, Q and X may condense to form a cyclic group. [3] The polymer of item [1] or [2], which further contains structural units represented by formula (1-4), In formula (1-4), R ²² is a hydrogen atom or an organic group having 1 to 3 carbon atoms. [4] The polymer according to any one of items [1] to [3], which further contains at least one selected from the structural unit represented by formula (1) and the structural unit represented by formula (2), In formula (1), R ^p is a group having two or more (meth)acrylyl groups, R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, In formula (2), R ^s is a group having one (meth)acrylyl group, and R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. [5] The polymer according to any one of items [1] to [4], which further contains a structural unit represented by formula (3), In formula (3), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. [6] The polymer of item [2], which further contains at least one selected from the structural unit represented by formula (8) and the structural unit represented by formula (9), In formula (8), Z is a group containing one or more (meth)acrylyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and X represents an oxygen atom or A substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. When Q is the aforementioned alkyl group and X is the aforementioned alkylene group, Q ^and (meth)acrylyl group, R ²¹ and R ²² are hydrogen atoms or organic groups with 1 to 3 carbon atoms, In formula (9), Z is a group containing one or more (meth)acrylyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and X represents an oxygen atom or an alkyl group having 1 to 6 carbon atoms. A substituted or unsubstituted alkylene group with 1 to 4 carbon atoms. When Q is the aforementioned alkyl group and X is the aforementioned alkylene group, Q ^and group) acrylic group, R ²¹ and R ²² are hydrogen atoms or organic groups having 1 to 3 carbon atoms. [7] The polymer of item [2], which further contains a structural unit represented by formula (5), In formula (5), Z is a group containing one or more (meth)acrylyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and X represents an oxygen atom or Substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. When Q is the aforementioned alkyl group and X is the aforementioned alkylene group, Q and X may be condensed to form a cyclic group. R ²¹ and R ²² are hydrogen atoms. Or an organic group having 1 to 3 carbon atoms. [8] The polymer of item [2], which further contains a structural unit represented by formula (6), In formula (6), Z is a group containing one or more (meth)acrylyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and X represents an oxygen atom or Substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. When Q is the aforementioned alkyl group and X is the aforementioned alkylene group, Q and X may be condensed to form a cyclic group. R ²¹ and R ²² are hydrogen atoms. Or an organic group having 1 to 3 carbon atoms. [9] The polymer according to any one of items [1] to [8], which further contains a structural unit represented by formula (MA), In the formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. [10] The polymer according to any one of items [1] to [9], wherein the polymer contains a structural unit represented by the aforementioned formula (1-2), and R ^p in the aforementioned formula (1-2) is at least one selected from the group consisting of the group represented by formula (1b), the group represented by formula (1c) and the group represented by formula (1d), In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and the plurality of R may be the same or different. X ¹ is a single bond, an alkylene group with 1 to 6 carbon atoms, or -ZX-. (Z is ^-O- or -OCO- ^, Alkylene group or a group represented by -X'-Z'- (X' is an alkylene group with 1 to 6 carbon atoms, Z' is -O- or -COO-), X ² is an alkylene group with 1 to 12 carbon atoms The organic radical with (k+1) valence, In formula (1c), k ^, R, X ¹ and X ² are respectively synonymous with R, k, ^{X 1 and} They may be the same or different from each other. X ³ is a single bond or a divalent organic group having 1 to 6 carbon atoms. X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms. ⁶ is a divalent organic group having 1 to 6 carbon atoms, In formula (1d), n is an integer of 2 to 5, and R is independently a hydrogen atom or a methyl group. [11] The polymer according to any one of items [1] to [10], wherein the polymer contains a structural unit represented by the aforementioned formula (1-3), and R ^s in the aforementioned formula (1-3) is the basis expressed by formula (2a), In formula (2a), X ¹⁰ is a divalent organic group, and R is a hydrogen atom or a methyl group. [12] The polymer according to any one of items [1] to [11], which further contains a structural unit represented by formula (MI), In the formula (MI), R ³¹ is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R ³² and R ³³ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. [13] The polymer according to any one of items [1] to [11], wherein the polymer has a structure represented by formula (P3), In formula (P3), n is an integer from 1 to 6, p, q and r represent the molar content of structural units A, B and C contained in each polymer chain within n [ ], p, q and r can be the same or different in each polymer chain within n [ ], p+q+r=1, p is 0 or more, q is 0 or more, r is 0 or more, if the polymer The molar content of each structural unit A, B and C contained in is set to p ^t , q ^t and r ^t respectively, then p ^t +q ^t +r ^t =1, p ^t is greater than 0, q ^t is greater than 0 , r ^t is greater than 0, X is a hydrogen atom or an organic group with 1 to 30 carbon atoms, Y is a 1-6 valent organic group with 1 to 30 carbon atoms derived from a monofunctional or difunctional or higher-functional thiol group-containing compound. , A represents the structural unit represented by the aforementioned formula (NB), and B contains at least one structural unit selected from the structural unit represented by the aforementioned formula (1-2) and the structural unit represented by the aforementioned formula (1-3). , C represents the structural unit represented by the aforementioned formula (AD), and there are a plurality of A's, B's, and C's which may be the same or different. [14] For example, the polymer of item [12] has a structure represented by formula (P4), In formula (P4), n is an integer from 1 to 6, p, q, r and s represent the molar content of structural units A, B, C and D contained in each polymer chain within n [ ] rate, p, q, r and s can be the same or different in each polymer chain within n [ ], p+q+r+s=1, p is 0 or more, q is 0 or more, r is 0 or more, s is 0 or more, if the molar content of each structural unit A, B, C and D contained in the polymer is respectively p ^t , q ^t , r ^t and s ^t , then p ^t +q ^t +r ^t +s ^t =1, p ^t is greater than 0, q ^t is greater than 0, r ^t is greater than 0, s ^t is greater than 0, X is a hydrogen atom or an organic group with 1 to 30 carbon atoms, Y is derived from A 1- to 6-valent organic group having a carbon number of 1 to 30 in a monofunctional or bifunctional or higher-functional thiol group-containing compound, A represents a structural unit represented by the aforementioned formula (NB), and B contains a member selected from the group consisting of the aforementioned formula (1-2 ) and at least one structural unit represented by the aforementioned formula (1-3), C represents the structural unit represented by the aforementioned formula (AD), D represents the structural unit represented by the aforementioned formula (MI) As for the structural unit, there are a plurality of A's, B's, C's and D's which may be the same or different. [15] The polymer according to any one of items [1] to [14], wherein the weight average molecular weight of the polymer is 2,000 or more and 20,000 or less. [16] A polymer solution containing the polymer of any one of items [1] to [15]. [17] The polymer solution of item [16], which further contains a multifunctional (meth)acrylic acid compound or a monofunctional (meth)acrylic acid compound or a combination thereof. [18] The polymer solution of item [16], which is used for the formation of color filters, black matrices, spacers or partition materials. [19] A photosensitive resin composition containing: the polymer according to any one of items [1] to [15]; and a photoradical polymerization initiator. [20] A hardened product formed from the photosensitive resin composition of item [19]. [21] A polymer containing: a structural unit represented by formula (NB); a structural unit represented by formula (AD); and a structural unit represented by formula (MA), wherein, In the general formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2, In formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, In the formula (AD), R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. . [22] The polymer of item [21], which further contains a structural unit represented by formula (MI), In the formula (MI), R ³¹ is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R ³² and R ³³ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. [23] The polymer of item [21], wherein the polymer has a structure represented by formula (P3'), In formula (P3'), n is an integer from 1 to 6, p, q' and r represent the molar content of structural units A, B' and C contained in each polymer chain within n [ ] , p, q' and r can be the same or different in each polymer chain within n [ ], p+q'+r=1, p is 0 or more, q' is 0 or more, r is 0 or more , if the molar content of each structural unit A, B and C contained in the polymer is set to p ^t , q ^t ' and r ^t respectively, then p ^t +q ^t '+r ^t =1, p ^t is greater than 0, ^{qt '} is greater than 0, rt is greater than 0, 30 is an organic group of 1 to 6 valence, A represents the structural unit represented by the aforementioned formula (NB), B' represents the structural unit represented by the aforementioned formula (MA), C represents the structural unit represented by the aforementioned formula (AD), There are a plurality of A's, B''s, and C's, which may be the same or different. [24] The polymer of item [22], wherein the polymer has a structure represented by formula (P4'), In formula (P4'), n is an integer from 1 to 6, p, q', r and s represent the structural units A, B', C and D contained in each polymer chain within n [ ]. Molar content, p, q', r and s can be the same or different in each polymer chain within n [ ], p+q'+r+s=1, p is 0 or more, q' is 0 or more, r is 0 or more, s is 0 or more, if the molar content of each structural unit A, B, C and D contained in the polymer is respectively set to p ^t , q ^t ', r ^t and s ^t , then p ^t +q ^t '+r ^t +s ^t =1, p ^t is greater than 0, q ^t ' is greater than 0, r ^t is greater than 0, s ^t is greater than 0, X is a hydrogen atom or the carbon number is 1~ 30 organic group, Y is a 1-6 valent organic group with 1 to 30 carbon atoms derived from a monofunctional or bifunctional or higher-functional thiol group-containing compound, A represents the structural unit represented by the aforementioned formula (NB), B ' represents the structural unit represented by the aforementioned formula (MA), C represents the structural unit represented by the aforementioned formula (AD), D represents the structural unit represented by the aforementioned formula (MI), and there are a plurality of A, B', and C and D may be the same or different from each other. [25] The polymer of item [20], wherein the softening point of the polymer is 60°C or more and 130°C or less. [Effects of the invention]

According to the present invention, it is possible to provide a product that has a low softening point or melting point and therefore is excellent in pattern formation after hardening, has high alkali solubility so that it is excellent in developability, and has reduced yellowing and therefore has high heat discoloration resistance for use in A polymer of resin material used in photosensitive resin compositions.

Hereinafter, embodiments of the present invention will be described. In addition, in all the drawings, the same components are denoted by the same symbols, and descriptions thereof are appropriately omitted. Also, all figures are for illustration only. The shape, size ratio, etc. of each member in the drawings do not necessarily correspond to the actual product. In this specification, the symbols "a to b" in the description of numerical ranges mean "a or more and b or less" unless otherwise specified. For example, "5 to 90%" means "more than 5% and less than 90%".

Among the symbols for groups (atomic groups) in this specification, symbols that do not indicate substituted or unsubstituted include both those that do not have a substituent and those that have a substituent. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

The symbol "(meth)acrylic acid" in this specification represents a concept that includes both acrylic acid and methacrylic acid. The same applies to "(meth)acrylate" and other similar marks. In particular, "(meth)acrylyl" in this specification means an acrylyl group represented by -C(=O)-CH= _CH2 and -C(=O)-C( _CH3 )=CH The concept of methacrylyl group represented by ₂ .

[Polymer P] The polymer of the present invention (referred to as "polymer P" in this specification) will be described. Unless otherwise specified, the structural units or compounds represented by the same structural formula in all embodiments have the same definition, and the preferred embodiments are also the same.

<First Embodiment> (Polymer P(I)) The polymer of the present invention according to the first embodiment (referred to as "polymer P(I)" in this specification) contains a structural unit represented by formula (NB); a structural unit represented by formula (AD); and At least one structural unit is selected from the structural units represented by formula (1-2) and the structural units represented by formula (1-3).

In the general formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In the formula (AD), R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. .

In formula (1-2), R ^p is a group having two or more (meth)acrylyl groups, and R ²² is a hydrogen atom or an organic group having 1 to 3 carbon atoms.

In formula (1-3), R ^s is a group having one (meth)acrylyl group, and R ²² is a hydrogen atom or an organic group having 1 to 3 carbon atoms.

The polymer P(I) of this embodiment has a structural unit derived from norbornene represented by formula (NB). The structural units derived from the norbornene monomer are chemically strong. Therefore, the polymer P(I) containing this as a structural unit loses little weight when subjected to heat treatment and is stable.

Moreover, the polymer P(I) of this embodiment has a structural unit derived from the unsaturated carboxylic acid dialkyl ester represented by Formula (AD). By introducing a structural unit (AD) derived from an unsaturated carboxylic acid dialkyl ester into the polymer P(I), the polymer P(I) can be reduced without causing changes in sensitivity, alkali solubility, and heat-resistant yellowing. ) softening point or melting point. Thereby, the polymer P(I) having the structural unit (AD) derived from the unsaturated dialkyl carboxylate is easily melted by heat when cured, and has excellent processability and pattern formation properties in photolithography processing. Therefore, in order to produce a film or a filter for use in a liquid crystal display device or a solid-state imaging element that requires heat resistance, a photosensitive resin composition containing polymer P(I) can be suitably used.

In the structural unit derived from unsaturated carboxylic acid dialkyl ester represented by formula (AD), the stereoconfiguration of -C(=O)-OR ¹¹ group and -C(=O)-OR ¹² group is not limited, It can be cis type or trans type. More specifically, as described in the following method for producing polymer P(I), the structural unit derived from unsaturated carboxylic acid dialkyl ester represented by formula (AD) may be derived from cis-type unsaturated The structure of the dialkyl dicarboxylate may also be derived from the structure of the trans-type unsaturated dialkyl dicarboxylate.

Moreover, the polymer P(I) of this embodiment contains the structural unit represented by formula (1-2) and/or the structural unit represented by formula (1-3). In other words, polymer P(I) contains any one or both of the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3). Thereby, the photosensitive resin composition containing polymer P(I) has excellent sensitivity when subjected to photolithography processing. This is considered to be because the (meth)acrylyl group contained in the structural unit represented by Formula (1-2) or Formula (1-3) accelerates the hardening reaction (polymerization reaction).

Among the structural units represented by the above formula (NB) constituting the polymer P (I), examples of organic groups having 1 to 30 carbon atoms constituting R ¹ to R ⁴ include saturated or unsaturated linear and branched ones. Chain or cyclic hydrocarbon groups having 1 to 30 carbon atoms, alkoxy groups, heterocyclic groups, carboxyl groups, etc. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, and the like.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, and heptyl. , octyl, nonyl and decyl, etc.

Examples of the alkenyl group include allyl, pentenyl, vinyl, and the like. Examples of the alkynyl group include an ethynyl group and the like. Examples of the alkylene group include methylene (methylidene), ethylene (ethylidene), and the like. Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups.

Examples of the aralkyl group include benzyl group, phenethyl group, and the like. Examples of the alkylaryl group include tolyl group, xylyl group, and the like. Examples of the cycloalkyl group include adamantyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, isobutoxy, tertiary butoxy, and n-pentoxy. Oxygen, neopentyloxy, n-hexyloxy, etc. Examples of the heterocyclic group include an epoxy group, an oxetanyl group, and the like.

R ¹ , R ² , R ³ and R ⁴ in the structural unit represented by formula (NB) are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. In addition, the hydrogen atom in the organic group having 1 to 30 carbon atoms in R ¹ , R ² , R ³ and R ⁴ may be substituted with any atomic group. For example, it may be substituted by a fluorine atom, a hydroxyl group, a carboxyl group, etc. More specifically, as the organic group having 1 to 30 carbon atoms in R ¹ , R ² , R ³ and R ⁴ , a fluorinated alkyl group or the like can be selected. In the structural unit represented by formula (NB), a ₁ is preferably 0 or 1, more preferably 0.

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

In the structural unit represented by the above formula (AD) constituting the polymer P (I), R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 12 carbon atoms. Examples of linear or branched alkyl groups having 1 to 12 carbon atoms as ^R11 and ^R12 in the structural unit of formula (AD) include methyl, ethyl, n-propyl, isopropyl, n- Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl Key et al. Among them, R ¹¹ and R ¹² are preferably linear or branched alkyl groups having 1 to 12 carbon atoms, because the obtained polymer P (I) does not impair the heat-resistant yellowness and has a low softening point or low melting point. In the structural unit represented by the above formula (AD) constituting the polymer P (I), R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, and isopropyl. From the viewpoint of reactivity, R ¹³ and R ¹⁴ are preferably hydrogen atoms.

The proportion of the structural units represented by the formula (AD) among all the structural units constituting the polymer P (I) is preferably 2 to 30 mol%, more preferably 3 to 28 mol%, and still more preferably 5 to 5 mol%. 25 mol%. By setting the ratio of the structural units represented by the formula (AD) in the polymer P (I) within the above range, it is possible to obtain a polymer having a low softening point or a low melting point and a balance of sensitivity, alkali solubility, and heat discoloration resistance. The level of polymer P(I) has been improved.

Polymer P (I) contains a structural unit represented by formula (1-2) containing two or more (meth)acrylyl groups (-C (=O)-CH=CH ₂ ) or formula (1-3 ) represents a structural unit containing one (meth)acrylyl group or a combination thereof. By containing such structural units, the polymer P(I) has more excellent sensitivity in exposure processing. This is considered to be because the (meth)acrylyl group contained in the structural unit represented by Formula (1-2) or Formula (1-3) accelerates the hardening reaction (polymerization reaction).

In the formula (1-2) or the formula (1-3), examples of the organic group having 1 to 3 carbon atoms that can constitute R ²² include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Both R ²¹ and R ²² are preferably hydrogen atoms.

In the structural unit represented by formula (1-2), R ^p is a group containing two or more (meth)acrylyl groups, preferably a group containing 2 to 9 (meth)acrylyl groups, and more preferably Preferably, it is a group containing 3 to 6 (meth)acrylyl groups. By optimally setting the number of (meth)acrylyl groups contained in R ^p , the sensitivity of the polymer P(I) containing it in the exposure process can be further improved. In addition, it is easy to achieve a higher degree of balance between the sensitivity and alkali solubility of the polymer P(I). In addition, the heat resistance of polymer P(I) can be improved.

R ^p in formula (1-2) is 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 using such a base, the above-mentioned various effects tend to be easily obtained.

In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and the plurality of R may be the same or different. X ¹ is a single bond, an alkylene group with 1 to 6 carbon atoms, or -ZX-. (Z is ^-O- or -OCO- ^, Alkylene group or a group represented by -X'-Z'- (X' is an alkylene group with 1 to 6 carbon atoms, Z' is -O- or -COO-), X ² is an alkylene group with 1 to 12 carbon atoms An organic radical with k+1 valence. From the viewpoint of further improving sensitivity (ease of polymerization), etc., R is preferably a hydrogen atom. k may be 2 or 3, but from the viewpoint of further improving the ease of acquisition of raw materials or sensitivity, 3 is preferred.

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

When X ¹ is a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group with 1 to 6 carbon atoms), the alkylene group with 1 to 6 carbon atoms in The chain shape may also be a branched chain shape. _The alkylene group having ₁ to 6 carbon atoms in ethyl) or -CH ₂ -CH (CH ₃ )-.

When X ¹ ' is an alkylene group having 1 to 6 carbon atoms, its specific aspect is the same as X ¹ . When X ¹ ' is the base represented by -X'-Z'-, the specific aspect of X' is the same as the above-mentioned X.

Examples of the (k+1)-valent organic group having 1 to 12 carbon atoms in X ² include any group obtained by removing (k+1) hydrogen atoms from any organic compound. The "arbitrary organic compound" here is, for example, an organic compound with 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 carbon atoms (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. Furthermore, the hydrocarbons here may contain oxygen atoms (for example, ether bonds or hydroxyl groups, etc.). Furthermore, the hydrocarbon is preferably a saturated hydrocarbon. As another aspect, 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, a group containing a heterocyclic structure (for example, an isocyanuric acid structure), and the like.

In formula (1c), k ^, R, X ¹ and X ² are respectively synonymous with R, k, ^{X 1 and} They may be the same or different from each other. X ³ is a divalent organic group having 1 to 6 carbon atoms. X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms. X ⁶ is carbon A divalent organic group with numbers 1 to 6.

The specific aspects, preferred aspects, etc. of R, k, X ¹ and X ² are the same as those explained in the formula (1b). Examples of the divalent organic group having 1 to 6 carbon atoms in X ³ and X ⁶ include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. Furthermore, the hydrocarbons here may contain oxygen atoms (for example, ether bonds or hydroxyl groups, etc.). Furthermore, the hydrocarbon is preferably a saturated hydrocarbon. Examples of the divalent organic groups having 1 to 6 carbon atoms in X ⁴ and X ⁵ include linear or branched alkylene groups. The carbon number of the linear or branched alkylene group is preferably 1 to 3.

In formula (1d), n is an integer from 2 to 5, preferably 2 or 3. The specific aspects, preferred aspects, etc. of R are the same as those explained in formula (1b).

When the polymer P (I) contains the structural unit represented by the formula (1-2), the proportion of the structural unit represented by the formula (1-2) among all the structural units of the polymer P (I) is preferably 3 ~40 mol%, more preferably 3 ~ 30 mol%.

Among the structural units represented by the formula (1-3) that can constitute the polymer P (I), R ^S is a group containing only one (meth)acrylyl group. In particular, in the design of ordinary photosensitive resin compositions, when curing properties are increased in order to increase sensitivity, curing proceeds excessively and the developability tends to deteriorate. On the other hand, when developability is improved in attempts to improve the curing properties, curing tends to becomes insufficient, so the polymer P(I) preferably contains either or both of the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), whereby , which can achieve both sensitivity and developability in a good balance.

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

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

As the divalent organic group of X ¹⁰ , a linear alkylene group having a total carbon number of 3 to 6 is more preferred. By appropriately selecting ^the carbon number of X ¹⁰ (the chain length of

The divalent organic group (eg, alkylene group) of X ¹⁰ may be substituted by any substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and the like. Furthermore, the divalent organic group of X ¹⁰ may be any group other than an alkylene group. For example, it may be a divalent group formed by linking one or two or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxyl group, and the like. .

When the polymer P (I) contains the structural unit represented by the formula (1-3), the proportion of the structural unit represented by the formula (1-3) among all the structural units of the polymer P (I) is preferably 5 ~30 mol%, more preferably 10 ~ 20 mol%.

Moreover, when the polymer P(I) contains both the structural unit represented by the formula (1-2) and the structural unit represented by the formula (1-3), the formula (1- in the polymer P(I) 2) The total proportion of the structural units represented and the structural units represented by formula (1-3) is based on all the structural units constituting the polymer P (I), preferably 5 to 40 mol%, more preferably 10 to 35 mol%, more preferably 15 to 30 mol%.

The polymer P(I) of this embodiment may contain a structural unit represented by formula (1-1) in addition to the above-mentioned structural units.

In the structural unit represented by formula (1-1), R ²¹ is a hydrogen atom or an organic group having 1 to 3 carbon atoms. ^RD is a group containing one or more (meth)acrylyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, and hexyl. Examples of the substituent of the substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group, and the like. X represents an oxygen atom and a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. Examples of the alkylene group constituting X include methylene, ethylene, propylene, and butylene. Examples of the substituent of the substituted alkylene group having 1 to 4 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group, and the like. When Q is the aforementioned alkyl group and X is the aforementioned alkylene group, any carbon atom in the alkyl group of Q and the alkylene group of X may be bonded to form a ring. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a benzene ring, a naphthalene ring, and the like. In formula (1-1), it is preferable to use an aspect in which X is an alkylene group having 1 to 4 carbon atoms and Z is a (meth)acryloxy group, or X is an oxygen atom and Z is (methyl) The form of acrylic group.

More specifically, in the formula (1-1), a state in which X is an alkylene group having 1 to 4 carbon atoms and Z is a (meth)acryloxy group represented by the following formula (1a) can be preferably used. Or X is an oxygen atom and Z is an acrylyl group (-C (=O)-CH=CH ₂ ) or a methacrylyl group (-C (=O)-C (CH ₃ ) =CH ₂ ) Like.

In formula (1a), R is a hydrogen atom or a methyl group.

When the polymer P (I) contains the structural unit represented by the formula (1-1), the proportion of the structural unit represented by the formula (1-1) among all the structural units of the polymer P (I) is preferably 0.5. ~20 mol%, more preferably 1 ~ 15 mol%.

Polymer P(I) may contain structural units represented by formula (1-4).

In formula (1-4), R ²² is a hydrogen atom or an organic group having 1 to 3 carbon atoms.

When the polymer P (I) contains the structural unit of the formula (1-1) and the structural unit of the formula (1-4), the polymer P (I) has a (meth)acrylyl group (formula (1-1) "-Z" group in) and the carboxyl group represented by formula (1-4). This (meth)acrylyl group contains a polymerizable carbon-carbon double bond. In this way, since the polymerizable group and the carboxyl group of the polymer P(I) exist in the same polymer molecule, the double bond equivalent and the acid value can be designed to be relatively large. Furthermore, in other resins such as (meth)acrylic resin, it is difficult to increase the contents of both polymerizable groups and carboxyl groups. By having such a structure, polymer P can achieve both sensitivity and developability at a high level.

The polymer P(I) may contain at least one selected from the structural unit represented by formula (1) and the structural unit represented by formula (2).

In Formula (1) and Formula (2), R ^p and R ^s and R ²¹ and R ²² are synonymous with those in the above-mentioned Formula (1-1), Formula (1-2) and Formula (1-4).

When the polymer P (I) contains the structural unit represented by the formula (1), the proportion of the structural unit represented by the formula (1) among all the structural units of the polymer P is preferably 0.5 to 25 mol%, more preferably Preferably, it is 1 to 18 mol%.

When the polymer P (I) contains the structural unit represented by the formula (2), the proportion of the structural unit represented by the formula (2) among all the structural units of the polymer P is preferably 0.5 to 35 mol%, more preferably Preferably, it is 2 to 25 mol%.

The polymer P(I) of this embodiment may contain the structural unit represented by Formula (3) in addition to the above-mentioned structural units. Polymer P(I) has high alkali solubility by containing the structural unit represented by formula (3). As a result, the photosensitive resin composition containing the polymer P(I) has excellent developability when used for photolithography using an alkali aqueous solution as a developer. The proportion of the structural units represented by the formula (3) among all the structural units of the polymer P (I) is preferably 1 to 10 mol%, more preferably 2 to 7 mol%.

In formula (3), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

The polymer P may contain at least one of the structural unit represented by formula (8) and the structural unit represented by formula (9). Here, the structural unit of formula (8) is a structural unit composed of the structural unit represented by formula (1-1) and the structural unit represented by formula (1-2), and the structural unit of formula (9) is composed of the formula A structural unit composed of the structural unit represented by (1-1) and the structural unit represented by formula (1-3).

In formula (8), Q, X, Z are synonymous with formula (1-1), and R ^p is synonymous with formula (1-2). In formula (9), Z, Q, and X are synonymous with formula (1-1), and R ^S is synonymous with formula (1-3).

When the polymer P (I) contains the structural unit represented by the formula (8), the proportion of the structural unit represented by the formula (8) among all the structural units of the polymer P (I) is preferably 0.25 to 17 moles. %, more preferably 0.5~12 mol%. When the polymer P (I) contains the structural unit represented by the formula (9), the proportion of the structural unit represented by the formula (9) among all the structural units of the polymer P (I) is preferably 0.25 to 17 moles. %, more preferably 0.5~12 mol%.

The polymer P(I) may contain a structural unit represented by the following formula (5) consisting of a structural unit represented by the formula (1-1) and a structural unit represented by the formula (1-4). By including this structural unit, it is possible to achieve both sensitivity and developability in a better balance.

In formula (5), Z, X, and Q are synonymous with formula (1-1) and formula (1-4). When the polymer P (I) contains the structural unit represented by the formula (5), the proportion of the structural unit represented by the formula (5) among all the structural units of the polymer P (I) is preferably 1 to 12 moles. %, more preferably 1 to 9 mol%.

From the viewpoint of the effects of the present invention, the polymer P (I) may further contain a structural unit represented by the following formula (6) consisting of two structural units represented by the formula (1-1). By including this structural unit, the sensitivity can be further improved.

In formula (6), Z, X, and Q are synonymous with formula (1-1) and formula (1-4). There are a plurality of Zs, a plurality of Qs, and a plurality of Xs, which may be the same or different.

When the polymer P (I) contains the structural unit represented by the formula (6), the proportion of the structural unit represented by the formula (6) among all the structural units of the polymer P (I) is preferably 1 to 10 moles. %, more preferably 1 to 8 mol%.

The polymer P(I) of this embodiment may contain a structural unit represented by formula (MA) in addition to the above-mentioned structural units. The structural unit represented by formula (MA) is ring-opened by an alkali developer to generate two carboxyl groups. Therefore, polymer P(I) has excellent developability. When the polymer P (I) contains the structural unit represented by the formula (MA), the structural unit represented by the formula (MA) in all the structural units of the polymer P (I) is preferably 3 to 40 mol%, More preferably, it is 10-30 mol%.

In the formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

In one embodiment, the polymer P (I) may contain, in addition to the above-mentioned structural units, a structural unit represented by the formula (MI).

In the formula (MI), R ³¹ is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R ³² and R ³³ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. In the structural unit represented by the formula (MI), examples of the organic group having 1 to 3 carbon atoms that can constitute R ³² and R ³³ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R ³² and R ³³ are preferably hydrogen atoms. Examples of the organic group having 1 to 30 carbon atoms that can constitute R ³¹ in formula (MI) include saturated or unsaturated linear, branched, or cyclic hydrocarbon groups and alkoxy groups having 1 to 30 carbon atoms. And heterocyclic groups and carboxyl groups, etc. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, and the like. R ³¹ is preferably a hydrocarbon group having 1 to 25 carbon atoms, more preferably a hydrocarbon group having 1 to 20 carbon atoms, even more preferably a hydrocarbon group having 1 to 15 carbon atoms.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, and heptyl. , octyl, nonyl and decyl, etc.

Examples of the alkenyl group include allyl, pentenyl, vinyl, and the like. Examples of the alkynyl group include an ethynyl group and the like. Examples of the alkylene group include methylene, ethylene, and the like. Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl, and anthracenyl.

Examples of the aralkyl group include benzyl group, phenethyl group, and the like. Examples of the alkylaryl group include tolyl group, xylyl group, and the like. Examples of the cycloalkyl group include adamantyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, isobutoxy, tertiary butoxy, and n-pentoxy. Oxygen, neopentyloxy, n-hexyloxy, etc. Examples of the heterocyclic group include an epoxy group, an oxycyclobutyl group, and the like.

R ³¹ in the structural unit represented by formula (MI) is preferably a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. By appropriately selecting R ³¹ , R ³² and R ³³ in the structural unit represented by formula (MI), especially selecting R ³¹ , the alkali solubility of the obtained polymer P (I) can be adjusted. For example, by setting R ³¹ as a hydrogen atom, the alkali solubility of the obtained polymer P(I) can be improved. Moreover, by setting R ³¹ as an alkyl group, a cycloalkyl group, or an aryl group, the alkali solubility of the obtained polymer P (I) can be suppressed. The substituents in the structural unit represented by the formula (MI) can be selected according to the desired alkali solubility in the use of the polymer P (I). In addition, the hydrogen atom in the organic group having 1 to 30 carbon atoms in R ³¹ may be substituted with any atomic group. For example, it may be substituted by a fluorine atom, a hydroxyl group, a carboxyl group, etc. More specifically, R ³¹ may be an organic group having 1 to 30 carbon atoms, and a fluorinated alkyl group or the like may be selected.

When the polymer P (I) contains the structural unit represented by the formula (MI), the proportion of the structural unit represented by the formula (MI) among all the structural units constituting the polymer P (I) is preferably 1 to 30 mol. mol%, more preferably 1.5 to 28 mol%, further preferably 2 to 25 mol%. By setting the proportion of the structural unit represented by the formula (MI) in the polymer P (I) within the above range, the sensitivity, alkali solubility and heat discoloration resistance of the polymer P (I) can be improved to a high level. balance.

The weight average molecular weight Mw of the polymer P(I) is, for example, 2,000 to 20,000. The weight average molecular weight Mw of the polymer P(I) is preferably 2,500 to 15,000, more preferably 3,000 to 10,000. By appropriately adjusting the weight average molecular weight, the sensitivity or the solubility to an alkali developer can be adjusted. Moreover, the dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) of the polymer P(I) of this embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and still more preferably 1.0 to 3.0. By appropriately adjusting the degree of dispersion, the physical properties of the polymer P can be made uniform, so this is preferable. Furthermore, these equivalent values can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard material.

The glass transition temperature of the polymer P(I) is preferably 100 to 250°C, more preferably 120 to 230°C. When it mainly contains the structural unit represented by the formula (NB), the glass transition temperature tends to be high. On the other hand, when it contains the structural unit represented by the formula (AD), the glass transition temperature tends to be low. The polymer P of this embodiment has a preferable glass transition temperature by containing the structural unit represented by formula (NB) and the structural unit represented by formula (AD). This is preferable from the viewpoint that the pattern formed on the substrate can stably exist when manufacturing a liquid crystal display device or a solid-state imaging element. In addition, the glass transition temperature can be calculated|required by differential thermal analysis (differential thermal analysis: DTA), for example.

The acid value of the polymer P(I) is 70 mgKOH/g or more and 150 mgKOH/g or less, preferably 80 mgKOH/g or more and 140 mgKOH/g or less. Moreover, the double bond equivalent of polymer P1 is 100g/mol or more and 900g/mol or less, Preferably it is 200g/mol or more and 850g/mol or less, More preferably, it is 200g/mol or more and 800g/mol or less. When the acid value of the polymer P(I) is 70 mgKOH/g or more, good developability can be obtained. In addition, when the double bond equivalent is 900 g/mol or less, the sensitivity of the photosensitive resin composition containing the polymer P(I) can be improved.

Furthermore, if the acid value of the polymer P(I) is too high, the exposed portion will be easily dissolved during development in an alkali developer, resulting in an increase in the amount of exposure required for photocuring, or an insufficient pattern shape. Yu. Therefore, in this embodiment, the upper limit of the acid value is set to 150 mgKOH/g. Furthermore, if the double bond equivalent of the polymer P(I) is too small (that is, if the density of double bonds in the polymer is too high), during development in an alkali developer, there will be unexposed areas or low-exposed areas. It tends to be difficult to dissolve and often produces residual film during development. In addition, if the double bond equivalent is too small, the molecular weight may be excessively increased by cross-linking and the solubility may be excessively decreased. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 100 g/mol.

By having the above-mentioned structure, the polymer P(I) of this embodiment can have an alkali dissolution rate of 20 nm/s or more, preferably 100 nm/s or more, more preferably 150 nm/s or more, particularly preferably 200nm/s and above. The upper limit is not particularly limited, but may be 2000 nm/s or less, for example. If the alkali dissolution rate is too fast, the developed pattern may not have the designed shape. In addition, in this specification, the alkali dissolution rate is the value measured under the following conditions. (Measurement method of alkali dissolution rate) Polymer P(I) was 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 was spin-coated on the wafer, and the PGMEA was dried and pre-baked at 100°C for 2 minutes to produce a resin film with a film thickness of 2 μm ± 0.2. The resin film and the wafer were immersed in a 2.0 mass% sodium carbonate aqueous solution at a temperature of 23°C. Visually observe the immersed wafer, measure the time until the resin film dissolves and no interference pattern is visible, and divide the film thickness before immersion (2 μm ± 0.2) by the time to calculate the alkali dissolution rate (μm/second).

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

The acid value and double bond equivalent of polymer P(I) can be determined by spectral measurement or the like. For example, it can be obtained by the following procedure (for more details, please refer to the embodiment). (1) From the ¹ H-NMR spectrum of the polymer, determine the area (integrated value) of the peak corresponding to the hydrogen atom of the carboxyl group or the hydrogen atom near the polymerizable carbon-carbon double bond. (2) For the area calculated in (1), determine the amount of carboxyl groups and the amount of carbon-carbon double bonds from the area of the peak derived from the standard material. (3) Convert the amount of carboxyl groups calculated in (2) into acid value (mgKOH/g). Furthermore, the amount of polymerizable carbon-carbon double bonds calculated in (2) is converted into double bond equivalent (g/mol).

The acid value and double bond equivalent of polymer P(I) can be appropriately designed by designing the ratio of structural units introduced into polymer P(I), especially the structure represented by formula (1) or formula (2). The number of polymerizable carbon-carbon double bonds contained in the (meth)acrylyl group contained in the unit is adjusted to the desired value.

The content (ratio) of each structural unit contained in the polymer P(I) of this embodiment can be determined according to the input amount (molar amount) of raw materials when synthesizing the polymer, the amount of raw materials remaining after synthesis, and various spectral The peak area (for example, the peak area of ¹ H-NMR), etc. is estimated/calculated.

The polymer P(I) of this embodiment has a low softening point of 110°C or less by containing the structural unit represented by formula (AD). The softening point of the polymer P(I) is preferably 100°C or lower, more preferably 90°C or lower. Moreover, the polymer P(I) of this embodiment has a low melting point of 130°C or less by containing the structural unit represented by formula (AD). The melting point of the polymer P(I) is preferably 120°C or lower, more preferably 110°C or lower. In addition, in this specification, the softening point and melting point of a polymer are the values measured under the following conditions. (Measurement method of softening point) 0.1 to 1.0 mg of the polymer to be measured was placed in an aluminum sample pan, and the softening point was measured using a differential thermal analysis device ("EXSTAR TMA/SS6100" manufactured by Hitachi High-Tech Science Corporation) in a nitrogen environment. The measurement mode was compression, the load was set to 30 mN, and the temperature was raised at a heating rate of 3°C/min in the range of 30°C to 200°C. If the sample softens due to temperature rise, the sample deforms, which is detected as the displacement amount (μm), the extension of the straight line portion without displacement on the low temperature side or the tangent line of the minimum portion of the displacement speed and the maximum displacement speed. The intersection point of the tangent lines of the parts is set as the softening point. (Measuring method of melting point) 1 to 2 mg of the polymer to be measured was placed in an aluminum sample pan, and a differential thermal analysis device (manufactured by Hitachi High-Technologies Corporation, "STA7200RV") was used in a nitrogen environment to observe the image from 30°C to 10°C. /min heating rate was carried out. The temperature at which the sample begins to melt is visually confirmed and used as the melting point.

(Method for manufacturing polymer P(I)) Polymer P(I) can be produced (synthesized) by any method. Typically, polymer P(I) can be produced by the following steps aI, step aII, and step aIII. Furthermore, in the following description of the manufacturing method of polymer P(I), for the sake of convenience, the obtained polymer P(I) contains the structural unit represented by formula (NB); formula (1- 2) The structural unit represented and/or the structural unit represented by formula (1-3); the polymer of the structural unit represented by formula (AD) is described. The raw material monomers can be selected according to the target structure of the polymer P(I). When the polymer P (I) contains the structural unit represented by the formula (MI), in step aI, the raw material monomer represented by the formula (IMm) can be used. Step aI: The step of preparing a raw material polymer containing the structural unit represented by formula (NB); the structural unit represented by formula (AD); and the structural unit represented by formula (MA); Step aII: The raw material polymer obtained in step aI is mixed with a compound having a hydroxyl group and two or more (meth)acrylyl groups (a polyfunctional (meth)acrylic acid compound) and/or a compound having a hydroxyl group and one (meth)acrylic acid group. A) acrylyl compound (monofunctional (meth)acrylic acid compound) is reacted in the presence of an alkaline catalyst to prepare a structural unit represented by formula (NB); a structural unit represented by formula (AD); And a polymer P(I) having 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) (sometimes referred to as "polymerization" Precursor (a)") steps. Here, the structural unit represented by formula (1) is a structural unit containing the structure of formula (1-2), and the structural unit represented by formula (2) is a structural unit containing the structure of formula (1-3).

In step aII, when both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used, it is preferred that the polyfunctional (meth)acrylic compound is first mixed with the polyfunctional (meth)acrylic compound obtained in step aI. The raw material polymer is reacted, and the monofunctional (meth)acrylic acid compound is reacted with the obtained reaction mixture.

When the polymer P(I) further contains a structural unit represented by formula (3), the following step aIII-i is performed. Step aIII-i: In step aII, prepare a product containing the structural unit represented by formula (NB); the structural unit represented by formula (AD); the structural unit represented by formula (1) and/or the structural unit represented by formula (2) Structural unit; and the polymer precursor (a) of the structural unit represented by formula (MA) (equivalent to the polymer P (I) in the above step aII), and then, the polymer precursor (a) is Treating with water in the presence of an alkali catalyst obtains a structural unit represented by formula (NB); a structural unit represented by formula (AD); a structural unit represented by formula (1) and/or a structural unit represented by formula (2) The structural unit of the polymer P(I) (sometimes referred to as the "polymer precursor (b)"); the structural unit represented by the formula (3); and the structural unit represented by the formula (MA). .

When the polymer P(I) further contains a structural unit represented by formula (1-1), the following step aIII-ii is performed. Step aIII-ii: Prepare the structural unit obtained in step aII containing the structural unit represented by formula (NB); the structural unit represented by formula (AD); the structural unit represented by formula (1) and/or formula (2) The structural unit represented by the formula (MA); and the polymer precursor (a) of the structural unit represented by the formula (MA) (equivalent to the polymer P (I) in the above step aII), so that the polymer precursor (a) is React with a (meth)acrylic acid compound containing an epoxy group in the presence of a catalyst to prepare a structural unit represented by formula (NB); a structural unit represented by formula (AD); a structure represented by formula (1) Units and/or structural units represented by formula (2); polymer P(I) of structural units represented by formula (1-1) and structural units represented by formula (MA). Here, the polymer P(I) obtained through step aII and the subsequent step aIII-ii may contain structural units represented by formula (8) and/or formula (9).

Either step aIII-i and step aIII-ii may be implemented. When both are implemented, it is preferred to implement step aIII-ii after step aIII-i. When step aIII-ii is implemented after step aIII-i, step aIII-ii is to make the polymer precursor (b) obtained in step aIII-i react with (methane) containing an epoxy group in the presence of a catalyst. base) acrylic compound to react to prepare a polymer P that may contain structural units represented by formula (8) and/or formula (9), structural units represented by formula (5) and structural units represented by formula (6) (I) Steps.

In step aII, when both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used, it is preferred that the polyfunctional (meth)acrylic compound is first mixed with the polyfunctional (meth)acrylic compound obtained in step aI. The raw material polymer is reacted, and the monofunctional (meth)acrylic acid compound is reacted with the obtained reaction mixture.

Each step is explained below. (Step aI) The step of preparing a raw material polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (AD) and a structural unit represented by formula (MA) in step aI can be achieved by making It is carried out by polymerizing (addition polymerization) a monomer composition of a monomer represented by formula (NBm), a monomer represented by formula (ADm), and a monomer represented by formula (MAm). Here, the definitions of R ¹ , R ² , R ³ , R ⁴ and a ¹ in the formula (NBm) are the same as those in the formula (NB). In addition, the definitions of R ¹¹ and R ¹² in the formula (ADm) are the same as those in the formula (AD). In addition, the definitions of R ²¹ and R ²² in the formula (MAm) are the same as those in the formula (MA). Furthermore, when the polymer P (I) contains the structural unit represented by the formula (MI), the raw material monomer represented by the formula (IMm) is used. Here, the definitions of R ³¹ , R ³² and R ³³ in the formula (MIm) are the same as those in the formula (MI).

Examples of the monomer represented by the formula (NBm) include norbornene, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), and 5-methyl-2-norbornene. Alkene, 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-phenylethyl-2-norbornene, 2-acetyl-5-norbornene, 5-norbornene-2-carboxylic acid methyl Ester, 5-norbornene-2,3-dicarboxylic anhydride, etc. During polymerization, only one type of monomer represented by formula (NBm) may be used, or two or more types may be used in combination.

In the unsaturated dicarboxylic acid dialkyl ester which is the monomer represented by the formula (ADm), the stereoconfiguration with respect to the double bond may be either a cis type or a trans type, and may be a trans type. Any of the monomer represented by the formula (t-ADm) or the monomer represented by the cis-type formula (c-ADm). Specific examples of the monomer represented by the formula (t-ADm) include dibutyl fumarate, diethyl fumarate, and bis(2-ethylhexyl fumarate). , dimethyl fumarate, etc. Examples of the monomer represented by the formula (c-ADm) include dibutyl maleate, diethyl maleate, and maleic acid. Acid bis(2-ethylhexyl), dimethyl maleate, etc.

The polymerization method is not limited, but radical polymerization using a radical polymerization initiator is preferred. As the polymerization initiator, for example, azo compounds, organic peroxides, etc. can be used. Specific examples of azo compounds include azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylpropionate)dimethyl ester, and 1,1'-azobis( Cyclohexanecarbonitrile) (ABCN), etc. Examples of organic peroxides include hydrogen peroxide, di(tertiary butyl) peroxide (DTBP), benzoyl peroxide (BPO), and methyl ethyl ketone peroxide (MEKP). wait. As for the polymerization initiator, only one type may be used, or two or more types may be used in combination.

As the solvent used in the polymerization reaction, organic solvents such as diethyl ether, tetrahydrofuran, toluene, and methyl ethyl ketone can be used. The polymerization solvent may be a single solvent or a mixed solvent.

The raw material polymer is synthesized by dissolving the monomer represented by the formula (NBm), the monomer represented by the formula (ADm), the monomer represented by the formula (MAm) and the polymerization initiator in a solvent and adding them The reaction vessel is then heated to perform addition polymerization. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours. The molar ratio (ADm+MAm) of the total amount of the monomer represented by the formula (NBm) and the monomer represented by the formula (ADm) and the monomer represented by the formula (MAm) when put into the reaction vessel is preferably (ADm+MAm). NBm): (ADm+MAm)=0.5:1～1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 0.5:0.8 to 0.7:0.5. The molar ratio between the monomer represented by the formula (ADm) and the monomer represented by the formula (MAm) is preferably (ADm): (MAm) = 0.5:9.5～8:2, more preferably 1:9～7: 4. Through such steps, the "raw material polymer" can be obtained. Furthermore, the base polymer may be any of random copolymers, alternating copolymers, block copolymers, periodic copolymers, and the like. Typically random copolymers or alternating copolymers. Furthermore, maleic anhydride is generally known to be a monomer with strong alternating copolymerizability.

Furthermore, after the raw material polymer is synthesized, a step of removing low molecular weight components such as unreacted monomers, oligomers, and remaining polymerization initiators may be performed. 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. Then, this solution is mixed with a poor solvent such as methanol, 2-propanol, and 1-butanol to precipitate the monomer. The purity of the raw material polymer can be improved by filtering out the precipitate and drying it.

(Step aII) In step aII, the raw material polymer obtained in step aI is reacted with a polyfunctional (meth)acrylic acid compound and/or a monofunctional (meth)acrylic acid compound in the presence of an alkaline catalyst. A part of the structural unit represented by the formula (MA) contained in the polymer is ring-opened to form the structural unit represented by the formula (1) and/or the structural unit represented by the formula (2), thereby obtaining a polymer containing the formula (NB). The structural unit represented, the structural unit represented by formula (AD) and the structural unit represented by formula (1) and/or the structural unit represented by formula (2) and, if applicable, the structural unit represented by formula (MA) of polymer precursors. The polymer precursor obtained here can be used as the polymer P(I) of this embodiment, and is called "polymer precursor (a)" for convenience of explanation.

More specifically, first, a solution in which the raw material polymer is dissolved in an appropriate organic solvent is prepared. As organic solvents, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethyl acetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF) can be used ) and other single solvents or mixed solvents, but are not limited to these, and various organic solvents used in the synthesis of organic compounds or polymers can be used.

When a polymer precursor containing both the structural unit represented by formula (NB), the structural unit represented by formula (AD), the structural unit represented by formula (1) and the structural unit represented by formula (2) is obtained When, next, add a polyfunctional (meth)acrylic acid compound to the above solution. Then add alkaline catalyst. Then, the solution is mixed appropriately to make it a uniform solution, and a polymer precursor containing at least the structural unit of formula (NB), the structural unit of formula (AD), and the structural unit of formula (1) is obtained (step aII-i ).

Examples of polyfunctional (meth)acrylic monomers that can be used here include compounds represented by general formula (1b-m), compounds represented by general formula (1c-m), and general formula (1d-m). the compound represented. The definitions and specific aspects of k, R, X ¹ , X ¹ ' and X ² in the formula (1b-m) are the same as those in the above formula (1b). In addition, the definitions and specific aspects ^{of k} , R, X ^{1 ,} X ² , X ³ , n and R in the formula (1d-m) are the same as those in the above formula (1d).

Next, the monofunctional (meth)acrylic acid compound is reacted with the polymer obtained in step aII-i in the presence of an alkaline catalyst, thereby obtaining a structural unit containing formula (NB), formula (AD) The structural unit of formula (1) and the polymer precursor of the structural unit of formula (2) (step aII-ii).

As the alkaline catalyst, amine compounds or nitrogen-containing heterocyclic compounds known in the field of organic synthesis can be appropriately used. For example, amine compounds such as triethylamine, pyridine, and dimethylaminopyridine or nitrogen-containing heterocyclic compounds can be used as the catalyst. The usage amount of the alkaline catalyst can be about 10 to 60 parts by mass relative to 100 parts by mass of the raw material polymer. Furthermore, it should be noted that if an alkaline catalyst is used excessively, the amount of acid required for neutralization will increase, and purification may become complicated.

The ring opening of the structural unit of the general formula (MA) contained in the base polymer and the formation of the structural unit of the formula (1) are performed by heating the above solution at preferably 60 to 80° C. for about 3 to 9 hours.

Furthermore, for example, during the above-mentioned heating, a monofunctional (meth)acrylic acid compound having a hydroxyl group is additionally added to the reaction system, whereby the structural unit of the formula (MA) contained in the raw material polymer is ring-opened. /The formation of the structural unit of formula (2), thereby producing the polymer P(I) having the structural unit represented by formula (2).

From the viewpoint of steric hindrance of reaction, etc., a monofunctional (meth)acrylic compound having a hydroxyl group tends to react with the raw material polymer more easily than a polyfunctional (meth)acrylic acid compound having a hydroxyl group. Therefore, when preparing a polymer precursor having a structural unit of formula (2), the monofunctional (meth)acrylic acid compound having a hydroxyl group is not put into the reaction system from the beginning, but is preferably added to the reaction system. in the system. Examples of the monofunctional (meth)acrylic compound having a hydroxyl group include compounds represented by the following formula (2a-m). In formula (2a-m), the definitions of X ¹⁰ and R are the same as those in formula (2a).

Specific examples of the compound represented by formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate. Meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(methyl)acrylate ) Acryloxyethyl-2-hydroxyethyl-phthalic acid, etc.

When a polymer containing any one of the structural unit represented by formula (NB), the structural unit represented by formula (AD), the structural unit represented by formula (1) and the structural unit represented by formula (2) is obtained In the case of a precursor, only step aII-i or step aII-ii may be performed after step (I).

(Step aIII-i) When implementing step aIII-i, the polymer precursor obtained in step aII is treated with water in the presence of an alkaline catalyst. By ring-opening the structural unit represented by formula (MA) contained in the polymer precursor obtained in step aII to form the structural unit represented by formula (3), it is possible to produce a polymer containing formula (NB) The structural unit represented by formula (AD); the structural unit represented by formula (1) and/or the structural unit represented by formula (2); and the aggregation of the structural unit represented by formula (3) Object P(I). When a part of the structural unit represented by formula (MA) is ring-opened and a part of the structural unit represented by formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA).

Examples of the alkaline catalyst used in step aIII-i include amine compounds such as triethylamine, pyridine, and dimethylaminopyridine or nitrogen-containing heterocyclic compounds.

In step aIII-i, water is added to the reaction system containing the polymer precursor obtained in step (II), and the obtained reaction solution is preferably heated at 60 to 80°C for about 0.25 to 6 hours. The structural unit of formula (MA) contained in the polymer is ring-opened to generate the structural unit represented by formula (3). The alkaline catalyst can be directly used as the catalyst remaining in the reaction system obtained in step aII. Therefore, regarding step aIII-i, it is preferable to perform it in situ by additionally adding water to the reaction mixture without performing any post-treatment on the reaction mixture obtained in step aII.

The polymer P(I) of this embodiment can be obtained through the above steps. However, from the viewpoint of the effects of the present invention, in order to remove unnecessary components other than the desired polymer, it may be further performed appropriately. Follow the steps below.

First, the reaction solution diluted with an organic solvent and added with an acid (such as formic acid, etc.) is vigorously stirred for at least 3 minutes using a separatory funnel. Let it stand for more than 30 minutes, separate into organic phase and aqueous phase, and remove the aqueous phase. In this way an organic solution of the polymer is obtained.

The obtained organic solution of polymer P(I) is purified using a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the obtained organic solution of polymer P(I) is added to excess toluene or water to reprecipitate the polymer. Furthermore, the polymer powder obtained by reprecipitating was washed several times with toluene or water. In addition, in order to remove formic acid or alkaline catalyst, the operation of washing the obtained polymer powder with ion-exchange water is repeated multiple times (about 1 to 3 times). A high-purity polymer can be obtained by drying the polymer powder washed with ion-exchange water at, for example, 30 to 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 for at least 3 minutes using a separatory funnel. Let it stand for more than 30 minutes, separate into organic phase and aqueous phase, and remove the aqueous phase. Furthermore, water was added to the organic solution of the polymer from which the water phase was removed, and the mixture was vigorously stirred for at least 3 minutes using a separatory funnel. Let it stand for more than 30 minutes, separate into organic phase and aqueous phase, and remove the aqueous phase. In this way an organic solution of the polymer is obtained. If necessary, further steps of adding water and removing the water phase can be performed. The obtained organic solution of polymer P (I) is heated under reduced pressure using a rotary evaporator to concentrate, and then the final solvent (PGMEA, etc.) is added and diluted repeatedly to obtain a solution dissolved in the final solution. Polymer solution in solvent. Moreover, after solvent replacement, further purification can be performed by reprecipitation.

Moreover, the polymer solution may contain the polyfunctional (meth)acrylic compound and/or the monofunctional (meth)acrylic compound used when synthesizing the polymer P(I). When the polymer solution contains these (meth)acrylic acid compounds, it is preferable that the peak area derived from the polyfunctional (meth)acrylic acid compound relative to the peak area of the polymer P in the gel permeation chromatography (GPC) spectrum becomes An amount of 3 to 50%, especially an amount of 5 to 48%, and preferably an amount in which the peak area derived from the monofunctional (meth)acrylic compound is 1 to 50% of the peak area of the polymer P, especially It becomes 2~35%. Thereby, the photosensitive resin composition containing the polymer solution has good alkali solubility and has good sensitivity in photolithography.

(Step aIII-ii) In step aIII-ii, by allowing the polymer (polymer precursor (a)) obtained in step aII or the polymer (polymer precursor (b)) obtained in step aIII-i to react in the catalyst The carboxyl group of the polymer precursor (a) or (b) is reacted with the epoxy group-containing (meth)acrylic acid compound in the presence of the epoxy group-containing (meth)acrylic acid compound to utilize the epoxy group The reaction forms the structural unit represented by formula (1-1), thereby enabling the manufacture to contain the structural unit represented by formula (NB); the structural unit represented by formula (AD); the structural unit represented by formula (1) and/or The structural unit represented by formula (2); and the polymer P(I) of the structural unit represented by formula (1-1). When a part of the structural unit represented by formula (MA) is ring-opened and a part of the structural unit represented by formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA).

Step aIII-ii is preferably implemented by additionally adding an epoxy group-containing (meth)acrylic acid compound to the reaction system containing the polymer precursor (b) obtained in step aIII-i.

The reaction between the polymer precursor (a) or (b) and the (meth)acrylic acid compound containing an epoxy group is carried out in the presence of an alkaline catalyst. The alkaline catalyst can be directly used as the catalyst remaining in the reaction system obtained in step aII. Therefore, regarding step aIII-ii, it is preferable not to separate and purify the polymer precursor from the reaction mixture containing the polymer precursor obtained in step aII or not to neutralize the alkaline catalyst contained in the mixture. And, it is implemented in situ by additionally adding an epoxy group-containing (meth)acrylic acid compound to the reaction mixture containing the polymer precursor obtained in step aII.

Specifically, the reaction solution obtained by additionally adding an epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor is preferably heated at 60 to 80° C. for about 1 to 9 hours. The reaction between the carboxyl group of the polymer precursor and the epoxy group of the (meth)acrylic compound containing an epoxy group forms a structural unit represented by the formula (1-1), thereby producing polymer P(I).

Examples of the (meth)acrylic compound containing an epoxy group include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), and 3,4-epoxycyclohexyl acrylate. Methyl ester, 3,4-epoxycyclohexylmethyl methacrylate, glycidyl acrylate, etc., one or two or more selected from these can be used.

The added amount of the (meth)acrylic compound containing an epoxy group is preferably 0.1 to 3.0 mol relative to 1 mol of the carboxyl group of the polymer precursor.

When the polymer P (I) is a polymer obtained through the polymer precursor (a), the polymer P (I) contains the structural unit represented by formula (AD); the structural unit represented by formula (8); The structural unit represented by formula (9); the structural unit represented by formula (1); the structural unit represented by formula (2).

When the polymer P (I) is a polymer obtained through the polymer precursor (b), the polymer P contains the structural unit represented by the formula (AD); the structural unit represented by the formula (8); the formula (9) ); the structural unit represented by formula (5); the structural unit represented by formula (6); the structural unit represented by formula (1); the structural unit represented by formula (2); the structural unit represented by formula (3) ) and the structural unit represented by formula (MA).

After step aIII-ii, in order to remove unnecessary components other than the desired polymer P(I), it is preferred to further perform the following steps appropriately.

First, the reaction solution diluted with an organic solvent and added with an acid (for example, formic acid, citric acid, etc.) is vigorously stirred for at least 3 minutes using a separatory funnel. Let it stand for more than 30 minutes, separate into organic phase and aqueous phase, and remove the aqueous phase. In this way an organic solution of polymer P(I) is obtained.

An excess amount of toluene was added to the obtained organic solution of polymer P(I) to reprecipitate polymer P(I). Moreover, the polymer powder obtained by reprecipitation is further washed several times (for example, twice) with toluene. In addition, in order to remove the acid or alkaline catalyst, the operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (for example, three times). By drying the polymer powder washed with ion-exchange water at, for example, 30 to 60° C. for 16 hours or more, the highly pure polymer P(I) of this embodiment can be obtained.

<Second Embodiment> (Polymer P(II)) The polymer in the second embodiment of the present invention (referred to as "polymer P(II)" in this specification) contains a structural unit represented by (NB); a structural unit represented by formula (AD); and optionally At least one structural unit from the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3) above, and has a structure represented by formula (P3). The polymer P (II) has a 1 to 6-valent organic group having a carbon number of 1 to 30 derived from a monofunctional or bifunctional or higher-functional thiol group-containing compound represented by "Y" in the formula (P3). There is a structure of a polymer chain typically composed of structural unit A, structural unit B and structural unit C. The 1-6 valent organic group having 1 to 30 carbon atoms derived from a monofunctional or bifunctional or higher-functional thiol group-containing compound is typically an organic group with 1 to 30 carbon atoms containing 1 to 6 thioether groups. .

In formula (P3), n is an integer from 1 to 6, p, q and r represent the molar content of structural units A, B and C contained in each polymer chain within n [ ], p, q and r can be the same or different in each polymer chain within n [ ], p+q+r=1, p is 0 or more, q is 0 or more, r is 0 or more, if the polymer The molar content of each structural unit A, B and C contained in is set to p ^t , q ^t and r ^t respectively, then p ^t +q ^t +r ^t =1, p ^t is greater than 0, preferably 0.25 ~0.75, more preferably 0.3~0.65, more preferably 0.35~0.60, q ^t is greater than 0, preferably 0.10~0.6, more preferably 0.2~0.50, more preferably 0.25~0.45, r ^t is greater than 0, preferably It is 0.03~0.3, more preferably 0.04~0.28, particularly preferably 0.05~0.25. X is a hydrogen atom or an organic group having 1 to 30 carbon atoms. Y is a 1-6 valent organic group having 1 to 30 carbon atoms derived from a monofunctional or bifunctional or higher-functional thiol group-containing compound. A is the structural unit represented by formula (NB). B contains at least one structural unit selected from the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3). C represents the structural unit represented by formula (AD). There are a plurality of A's, B's and C's which may be the same or different.

In one embodiment, the polymer P (II) may further contain a structural unit represented by the formula (MI), and in this case, has a structure represented by the formula (P4).

In the formula (P4), n, X, Y, A, B, and C are synonymous with those in the above formula (P3). p, q, r and s represent the molar content of structural units A, B, C and D contained in each polymer chain within n [ ], p, q, r and s are in n [ ] Each polymer chain in can be the same or different, p+q+r+s=1, p is 0 or more, q is 0 or more, r is 0 or more, s is 0 or more, if the polymer is The molar content of each structural unit A, B, C and D is set to p ^t , q ^t , r ^t and s ^t respectively, then p ^t +q ^t +r ^t +s ^t =1, p ^t Greater than 0, q ^t is greater than 0, r ^t is greater than 0, s ^t is greater than 0, p ^t is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, more preferably 0.35 to 0.60. q ^t is greater than 0, preferably 0.10 to 0.6, more preferably 0.2 to 0.50, more preferably 0.25 to 0.45. r ^t 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. s ^t is greater than 0, preferably 0.01 to 0.3, more preferably 0.015 to 0.28, and particularly preferably 0.02 to 0.25. D represents the structural unit represented by formula (MI). There are a plurality of A's, B's, C's and D's which may be the same or different.

The polymer P(II) represented by the formula (P3) or the formula (P4) may contain the structural unit represented by the above formula (1-1) as the structural unit B. The polymer P(II) represented by the formula (P3) or the formula (P4) may contain the structural unit represented by the above formula (1-4) as the structural unit B. The polymer P (II) represented by the formula (P3) or the formula (P4) may contain at least one selected from the structural unit represented by the above formula (1) and the structural unit represented by the formula (2) as a structural unit. B. The polymer P(II) represented by the formula (P3) or the formula (P4) may contain the structural unit represented by the above formula (3) as the structural unit B. The polymer P(II) represented by the formula (P3) or the formula (P4) may contain at least one selected from the structural unit represented by the above-mentioned formula (8) and the structural unit represented by the formula (9) as a structural unit. B. The polymer P(II) represented by the formula (P3) or the formula (P4) may contain the structural unit represented by the above formula (5) as the structural unit B. The polymer P(II) represented by the formula (P3) or the formula (P4) may contain the structural unit represented by the above formula (6) as the structural unit B. The polymer P(II) represented by the formula (P3) or the formula (P4) may contain the structural unit represented by the above formula (MA) as the structural unit B.

In formula (P3) or formula (P4), X is a hydrogen atom or an organic group having 1 to 30 carbon atoms. The organic group having 1 to 30 carbon atoms is the same as the organic group having 1 to 30 carbon atoms that can constitute R ¹ in the above formula (NB).

In formula (P3) or formula (P4), Y is a 1-6 valent organic group having 1 to 30 carbon atoms derived from a monofunctional or bifunctional or higher-functional thiol group-containing compound (herein referred to as " Organic base (i)"). In this embodiment, the acid value is the number of functional groups (the number of thiol groups). That is, the monofunctional or bifunctional or higher-functional thiol group-containing compound contains one or more thiol groups, and the organic group (i) is separated from 1 to 6 thioether groups derived from the thiol group. The structural units in [ ]n and the structural units in [ ]m are bonded. The organic group (i) may also have a thiol group that does not participate in the bonding with the structural units in [ ]n and the structural units in [ ]m. The polymer P (I) can be in the number of (n+m) ( The number of bonds) is obtained as a mixture of individual resins ranging from 1 to 6. The organic group (i) having 1 to 30 carbon atoms is monofunctional or bifunctional or higher, preferably bifunctional or higher, more preferably trifunctional or higher. The upper limit is not particularly limited, but is 6 functional or less. From the viewpoint of the effect of the present invention, the valence of the organic group (i) having 1 to 30 carbon atoms is, for example, 1 to 6 valences, preferably 2 to 6 valences, and more preferably 3 to 6 valences.

The 1- to 6-valent 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 1 to 6-valent organic group (i) having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, and an alkynyl group having 1 to 6 thioether groups (-S-* (* represents a bond)). , alkylene, aryl, aralkyl, alkaryl, cycloalkyl, alkoxy and heterocyclyl.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, and heptyl. , octyl, nonyl and decyl. Examples of the alkenyl group include allyl, pentenyl and vinyl.

Examples of the alkynyl group include an ethynyl group. Examples of the alkylene group include methylene and ethylene. Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl and anthracenyl. Examples of the aralkyl group include benzyl group and phenethyl group. Examples of the alkaryl group include tolyl group and xylyl group.

Examples of the cycloalkyl group include adamantyl, cyclopentyl, cyclohexyl and cyclooctyl. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, isobutoxy, tertiary butoxy, and n-pentoxy. Oxygen, neopentyloxy and n-hexyloxy. Examples of the heterocyclic group include an epoxy group and an oxycyclobutyl group.

Examples of the monofunctional or bifunctional or higher-functional thiol group-containing compound from which Y can be derived in Formula (P3) or Formula (P4) include compounds represented by the following chemical formulas (s-1) to (s-21). That is, the polymer P (II) contains a 1- to 6-valent organic group (i) having a carbon number of 1 to 30 derived from a monofunctional or bifunctional or higher-functional thiol group-containing compound represented by the following.

One type of monofunctional or two or more functional thiol group-containing compounds may be used alone, or two or more types may be mixed and used. Among them, a 3- to 6-functional (3- to 6-valent) thiol group-containing compound having 3 to 6 thiol groups in one molecule is preferred from the viewpoint of excellent reactivity with other monomers. In this embodiment, among the compounds represented by the aforementioned chemical formulas (s-1) to (s-21), the monofunctional or bifunctional or higher-mentioned thiol group-containing compound more preferably contains the chemical formula (s-1) The compounds represented by ~(s-3), (s-5) and (s-8) ~ (s-10) are particularly preferably compounds containing chemical formulas (s-1) ~ (s-3), (s- 5) and the compound represented by (s-9). The 1 to 6-valent organic group (i) having 1 to 30 carbon atoms has a thioether group (-S-* (* is a connecting bond)) derived from the thiol group of the thiol group-containing compound at the terminal, and The thioether group is bonded to the structural unit in [ ]n and the structural unit in [ ]m. The aforementioned organic group (i) may also have a thiol group that does not participate in the bonding with the structural unit in [ ]n and the structural unit in [ ]m.

When the polymer P (II) of this embodiment has a structure represented by formula (P3) and a tetrafunctional (tetravalent) thiol group-containing compound represented by the above formula (s-2) is used as a monofunctional or bifunctional When polymer P(II) is obtained from the above thiol group-containing compound, polymer P(II) may have a structure represented by the following formula (I).

In formula (I), A, B, C, X, p, q and r are synonymous with those in formula (P3). In formula (I), for the sake of explanation, p, q and r of each polymer chain within four [ ] are respectively described as p ¹ to p ⁴ , q ¹ to q ⁴ , r ¹ to r ⁴ . In formula (I), p ¹ to p ⁴ , q ¹ to q ⁴ , r ¹ to r ⁴ may be the same or different in each of the four polymer chains [ ], and p ¹ +q ¹ +r ¹ =1, p ² +q ² +r ² =1, p ³ +q ³ +r ³ =1, p ⁴ +q ⁴ +r ⁴ =1. If the molar content of each structural unit A, B and C contained in the polymer represented by formula (I) is p ^t , q ^t and r ^t respectively, then p ^t =p ¹ +p ² + p ³ +p ⁴ , q ^t =q ¹ +q ² +q ³ +q ⁴ , r ^t =r ¹ +r ² +r ³ +r ⁴ .

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

The physical properties such as weight average molecular weight Mw, dispersion (weight average molecular weight Mw/number average molecular weight Mn), glass transition temperature, softening point, melting point, acid value, double bond equivalent and alkali dissolution rate of polymer P(II) are related to the above polymerization The physical properties of object P(I) are the same.

(Production method of polymer P(II)) Polymer (A) can be produced (synthesized) by any method. Typically, polymer P(II) can be produced by the following steps bI, step bII, and step bIII. Furthermore, in the following description of the manufacturing method of polymer P(II), for the sake of convenience, the obtained polymer P(I) contains the structural unit represented by formula (NB); formula (1- 2) The structural unit represented and/or the structural unit represented by formula (1-3); the polymer of the structural unit represented by formula (AD) is described. The raw material monomers can be selected according to the target structure of the polymer P(II). When the polymer P (II) contains the structural unit represented by the formula (MI), in step bI, the raw material monomer represented by the formula (IMm) can be used. Step bI: Prepare an organic group (i) containing a structural unit represented by the formula (NB), a structural unit represented by the formula (AD), a structural unit represented by the formula (MA), and a 1- to 6-valent organic group having 1 to 30 carbon atoms. ) steps of raw material polymer; Step bII-i: The raw material polymer obtained in step bI is mixed with a compound having a hydroxyl group and two or more (meth)acrylyl groups (a polyfunctional (meth)acrylic acid compound) and/or a compound having a hydroxyl group and one or more (meth)acrylyl groups. A (meth)acrylyl compound (monofunctional (meth)acrylic acid compound) is reacted in the presence of an alkaline catalyst to prepare a structure containing a structural unit represented by formula (NB) and a structure represented by formula (AD) unit, a 1- to 6-valent organic group (i) having 1 to 30 carbon atoms, 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) The step of representing the first polymer precursor (IIa) of the structural unit.

When the polymer P(II) further contains the structural unit represented by formula (3), the following step bIII-i is performed. Step bIII-i: In step bII, prepare a product containing the structural unit represented by formula (NB), the structural unit represented by formula (AD), the structural unit represented by formula (1) and/or the structural unit represented by formula (2) The polymer precursor of the structural unit and the structural unit represented by formula (MA) (equivalent to the polymer P (II) in the above step bII), and then the polymer precursor is heated in the presence of an alkali catalyst A step of treating with water to obtain polymer P(II).

In step bII, when both a multifunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used, it is preferred that the multifunctional (meth)acrylic compound is first mixed with the compound obtained in step bI. The raw material polymer is reacted, and the monofunctional (meth)acrylic acid compound is reacted with the obtained reaction mixture.

When the polymer P(II) further contains a structural unit represented by formula (1-1), the following step bIII-ii is performed. Step bIII-ii: Prepare the structural unit represented by formula (NB), the structural unit represented by formula (AD), the structural unit represented by formula (1) and/or the structural unit represented by formula (2) obtained in step bII The polymer precursor of the structural unit represented by the structural unit represented by the formula (MA) (equivalent to the polymer P (II) in the above step bII), so that the polymer precursor reacts with the polymer precursor containing the ring in the presence of a catalyst. A step of preparing polymer P(II) by reacting an oxy(meth)acrylic acid compound.

Either of step bIII-i and step bIII-ii may be implemented. When both are implemented, it is preferred to implement step bIII-ii after step bIII-i.

Each step is explained below. (step bI) The preparation in step bI contains a structural unit represented by the formula (NB), a structural unit represented by the formula (AD), a structural unit represented by the formula (MA) and a 1-6 valent organic group having 1 to 30 carbon atoms ( The step of the raw material polymer of i) can be performed by making the monomer composition containing the monomer represented by the formula (NBm), the monomer represented by the formula (ADm) and the monomer represented by the formula (MAm) in the monofunctional Or polymerization (addition polymerization) is carried out in the presence of a bifunctional or higher-functional thiol group-containing compound.

Examples of the monofunctional or bifunctional or higher-functional thiol group-containing compound include compounds represented by the aforementioned chemical formulas (s-1) to (s-21), but are not limited thereto. One type of monofunctional or two or more functional thiol group-containing compounds may be used alone, or two or more types may be mixed and used. The specific conditions of step bI are the same as step aI in the method for producing polymer P(I) according to the first embodiment.

(Step bII) The same conditions as those of step aII in the method for producing polymer P(I) according to the first embodiment can be applied to step bII.

(Step bIII-i) The same conditions as those of step aIII-i in the method for producing polymer P(I) according to the first embodiment can be applied to step bIII-i. (Step bIII-i) The same conditions as those of step aIII-ii in the method for producing polymer P(I) according to the first embodiment can be applied to step bIII-ii.

＜Third Embodiment＞ (Polymer P(III)) The polymer P (hereinafter, referred to as "polymer P (III)") in the third embodiment contains a structural unit represented by formula (NB), a structural unit represented by formula (AD), and a structural unit represented by formula (MA). the structural unit.

In the general formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In the formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

In the formula (AD), R ¹¹ and R ¹² are each independently a linear or branched chain alkyl group having 1 to 12 carbon atoms, and -C (=O) -OR ¹¹ group and -C (=O) -OR ¹² R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The greater the number of carbon atoms in R ¹¹ and R ¹² , the lower the softening point and melting point of polymer P(III) tend to be.

The polymer P(III) is the raw material polymer used for producing the polymer P(I) in the first embodiment, and is the polymer obtained in the step aI described above.

Polymer P(III) has a low softening point of 130° C. or lower by containing a structural unit represented by formula (AD). The softening point of the polymer P(III) is preferably 125°C or lower, more preferably 120°C or lower. In addition, the polymer P (III) has a low melting point of 160° C. or less by containing the structural unit represented by the formula (AD). The melting point of the polymer P(III) is preferably 155°C or lower, more preferably 150°C or lower.

The weight average molecular weight Mw of the polymer P(III) is, for example, 1,000 to 5,000. The weight average molecular weight Mw of the polymer P(III) is preferably 1,000 to 4,500. By appropriately adjusting the weight average molecular weight, the weight average molecular weight of the polymer P(I) obtained from the polymer P(III) can be adjusted. As a result, the sensitivity of the polymer P(III) or the resistance to an alkali developer can be improved. The solubility is adjusted to the desired level. Furthermore, the dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) of the polymer P (III) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and still more preferably 1.0 to 3.0.

<Fourth Embodiment> (Polymer P(IV)) The polymer in the fourth embodiment of the present invention (referred to as "polymer P(IV)" in this specification) has a structural unit represented by formula (NB), a structural unit represented by formula (MA) and a formula The structural unit represented by (AD) and has the structure represented by formula (P3'). Polymer P (IV) has a 1- to 6-valent organic group bond with a carbon number of 1 to 30 derived from a monofunctional or bifunctional or higher-functional thiol group-containing compound represented by "Y" in the formula (P3') The knot has a structure of a polymer chain typically composed of structural units A, B and C. The 1-6 valent organic group having 1 to 30 carbon atoms derived from a monofunctional or bifunctional or higher-functional thiol group-containing compound is typically an organic group with 1 to 30 carbon atoms containing 1 to 6 thioether groups. .

In formula (P3'), n is an integer from 1 to 6, p, q' and r represent the molar content of structural units A, B' and C contained in each polymer chain within n [ ] , p, q' and r can be the same or different in each polymer chain within n [ ], p+q'+r=1, p is 0 or more, q' is 0 or more, r is 0 or more , if the molar content of each structural unit A, B and C contained in the polymer is set to p ^t , q ^t ' and r ^t respectively, then p ^t +q ^t +r ^t =1, p ^t is greater than 0, preferably 0.25~0.75, more preferably 0.3~0.65, more preferably 0.35~0.6, ^qt ' is greater than 0, preferably 0.25~0.75, more preferably 0.3~0.65, more preferably 0.35~0.60 , r ^t is greater than 0, preferably 0.05 to 0.70, more preferably 0.06 to 0.65, more preferably 0.07 to 0.60, Y is a compound with 1 to 30 carbon atoms derived from a monofunctional or bifunctional or higher-functional thiol group-containing compound. Organic groups with 1 to 6 valences, A represents the structural unit represented by formula (NB), B' represents the structural unit represented by formula (MA), C represents the structural unit represented by formula (AD), and there is a plurality of A Each other, B' each other, and C each other may be the same or different.

In one embodiment, the polymer P (IV) may contain a structural unit represented by the formula (MI), and in this case, has a structure represented by the formula (P4').

In the formula (P4'), n, X, Y, A, B', and C are synonymous with those in the above formula (P3'). p, q', r and s represent the molar content of structural units A, B', C and D contained in each polymer chain within n [ ], p, q', r and s are in n Each polymer chain in [ ] can be the same or different, p+q'+r+s=1, p is 0 or more, q' is 0 or more, r is 0 or more, s is 0 or more, if Let the molar content of each structural unit A, B', C and D contained in the polymer be p ^t , q ^t ', ^rt and s ^t respectively, then p ^t +q ^t '+r ^t +s ^t =1, p ^t is greater than 0, q ^t ' is greater than 0, r ^t is greater than 0, s ^t is greater than 0, p ^t is greater than 0, preferably 0.25~0.75, more preferably 0.3~0.65, more preferably 0.35 ~0.60. q ^t ' is greater than 0, preferably 0.10 to 0.6, more preferably 0.2 to 0.50, more preferably 0.25 to 0.45. r ^t 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. s ^t is greater than 0, preferably 0.01 to 0.3, more preferably 0.015 to 0.28, and particularly preferably 0.02 to 0.25. D represents the structural unit represented by formula (MI). There are a plurality of A's, B's, C's and D's which may be the same or different.

Polymer P(IV) is the raw material polymer used in the production of the above-mentioned polymer P(II), and is the polymer obtained in the step bI above.

The weight average molecular weight Mw and dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) of the polymer P (IV) are the same as the physical properties of the above-mentioned polymer P (III).

[Polymer solution] The polymer solution of this embodiment contains the above-mentioned polymer P(I) or polymer P(II). The polymer solution of this embodiment contains polymer P(I) or polymer P(II), and contains at least one selected from the group consisting of polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds.

[Polyfunctional (meth)acrylic compound] The polyfunctional (meth)acrylic acid compound or the monofunctional (meth)acrylic acid compound that may be contained in the polymer solution of this embodiment may be the (methyl) compound used in the above-mentioned step aII or step bII when producing the polymer P. The unreacted product of the acrylic compound may be additionally added.

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

The definitions and specific aspects of k, R, X ¹ , X ¹ ' and X ² in the formula (1b-p) are the same as those in the above formula (1b). In addition, the definitions and specific aspects of ^k , R ^, X ^{1 ,} X ² , X ³ ,

Y in formula (1b-p), formula (1c-p) and formula (1d-p) is a hydrogen atom or a (meth)acrylyl group or a combination thereof.

The compound in which Y is a hydrogen atom in formula (1b-p), formula (1c-p) and formula (1d-p) can be an unreacted monomer (that is, formula (1b-p), formula (1c-p) and compounds represented by formula (1d-p)), which can also be added additionally. n in the formula (1d-p) is an integer of 2 or more, preferably an integer of 2 to 5, more preferably an integer of 2 to 3.

When the polyfunctional (meth)acrylic compound is separately blended with the unreacted product of the polyfunctional (meth)acrylic compound used in the production of the polymer P(I) or the polymer P(II) in the polymer solution of this embodiment, When a polyfunctional (meth)acrylic compound is used, the blending amount may be based on the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) spectrum of the polymer solution relative to the polymer P(I) or The peak area of the polymer P(II) is preferably 10% or less, more preferably 5% or less, and still more preferably 2% or less.

[Monofunctional (meth)acrylic compound] Examples of the monofunctional (meth)acrylic compound blended in the polymer solution of this embodiment include compounds represented by the following formulas (2a-m). In formula (2am), the definitions of X ¹⁰ and R are the same as those in formula (2a).

When the unreacted product of the monofunctional (meth)acrylic compound used in the production of the polymer P(I) or the polymer P(II) is separately blended with the polymer solution of the present embodiment, the monofunctional (meth)acrylic compound base) acrylic compound, its blending amount can be based on the peak area from the monofunctional (meth)acrylic compound in the gel permeation chromatography (GPC) spectrum of the polymer solution relative to the polymer P (I) or The peak area of the polymer P(II) is preferably 10% or less, more preferably 5% or less, and still more preferably 2% or less.

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

Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, and the like. One type of these may be used alone, or two or more types may be used in combination. The usage amount of the organic solvent is not particularly limited, but it is used in an amount such that the concentration of the non-volatile component becomes, for example, 10 to 70 mass %, preferably 15 to 60 mass %.

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

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

(Photopolymerization Initiator) Examples of the photopolymerization initiator used in the photosensitive resin composition of this embodiment include photoradical polymerization initiators. As the photoradical polymerization initiator, well-known compounds can be used, and examples thereof include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxyl acetophenone. Cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl -1-Propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropyl)benzyl]phenyl}-2-methylpropan-1-one , 2-methyl-1-(4-methylthiophenyl)-2- Oxylinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phylinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Alkylphenone compounds such as pholinyl)phenyl]-1-butanone; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxydiphenyl Benzophenone compounds such as methyl ketone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin compounds; 9-oxosulfide𠮿 (thioxanthone), 2-ethyl-9-oxanthone𠮿 , 2-isopropyl-9-oxosulfide𠮿 , 2-chloro-9-oxosulfide𠮿 2,4-Dimethyl-9-oxosulfide𠮿 , 2,4-diethyl-9-oxosulfide𠮿 Etc-9-oxysulfur𠮿 Compounds; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)symmetric trichloromethyl, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) Methyl) symmetric tri𠯤, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl) symmetric tri𠯤, 2-(4-ethoxycarbonylnaphthyl)-4,6 - Bis (trichloromethyl) symmetric tris and other halomethylated tris compounds; 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-diadiazole, 2-Trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5- Furyl-1,3,4-ethadiazole and other halomethylated ethadiazole compounds; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl -1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2, 2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and other biimidazole compounds; 1,2-octanediazole Ketone, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl oxime) )-9H-carbazol-3-yl]-1-(O-acetyl oxime) and other oxime ester compounds; bis(eta5-2,4-cyclopentadien-1-yl)-bis(2,6 - Titanium-based compounds such as difluoro-3-(1H-pyrrol-1-yl)-phenyl) titanium; benzoate compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid ; 9-phenylacridine and other acridine compounds, etc. One type of photoradical polymerization initiator may be used alone, or two or more types may be used in combination. 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, based on 100 parts by mass of the polymer P.

By containing the above components, the photosensitive resin composition of this embodiment has high sensitivity in photolithography processing and has excellent alkali solubility. Therefore, the photosensitive resin composition has excellent developability and excellent processability in photolithography.

(colorant) As one aspect, the photosensitive resin composition may contain a colorant. By containing a colorant, it can be suitably used as a forming material for a color filter of a liquid crystal display device or a solid-state imaging element. As the colorant, various pigments or dyes can be used. As the pigment, organic pigments or inorganic pigments can be used.

As organic pigments, azo pigments, phthalocyanin pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, and isoindoline pigments can be used. ) pigments, dimethacin pigments, thioindigo pigments, anthraquinone pigments, quinoline yellow pigments, metal complex pigments, diketo-pyrrolo-pyrrole pigments ,𠮿 (xanthene) pigments, pyrromethene (pyrromethene) pigments, dye lake pigments, etc.

As inorganic pigments, white/extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), colored pigments (chrome yellow, cadmium series, chrome vermilion, nickel titanium) can be used , chromium titanium, yellow iron oxide, hematite oxide (Bengala), zinc chromate, lead red, ultramarine blue, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), brightening material pigments (pearlescent pigments , aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

As the dye, for example, known dyes described in Japanese Patent Application Laid-Open No. 2003-270428, Japanese Patent Application Laid-Open No. 9-171108, Japanese Patent Application Laid-Open No. 2008-50599, etc. can be used. When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one colorant, or may contain two or more colorants.

Colorants (especially pigments) having an appropriate average particle size can be used depending on the purpose or use. When transparency such as a color filter is particularly required, a small average particle size of 0.1 μm or less is preferred. In addition, when When hiding properties of coatings, etc. are required, a large average particle diameter of 0.5 μm or more is preferred.

The colorant can be subjected to surface treatment such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose or use.

When the photosensitive resin composition contains a colorant, its amount can be appropriately set according to the purpose or use. However, from the viewpoint of balancing the coloring concentration and the dispersion stability of the colorant, relative to the non-volatile components of the photosensitive resin composition The total amount (components other than solvent) is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and still more preferably 10 to 50 mass %.

(surfactant) The photosensitive resin composition of this embodiment may contain a surfactant, and the surfactant is preferably a nonionic surfactant.

By containing a nonionic surfactant, the coating property when applying the photosensitive resin composition to a base material to obtain a resin film becomes good, and a coating film with a uniform thickness can be obtained. Furthermore, it is possible to prevent residues and pattern floating during development of the coating film.

Nonionic surfactants are, for example, compounds containing fluorine groups (eg, fluorinated alkyl groups) or silanol groups, or compounds with siloxane bonds as the main skeleton. In this embodiment, as the nonionic surfactant, one containing a fluorine-based surfactant or a polysiloxane-based surfactant is more preferably used, and a fluorine-based surfactant is particularly preferably used. Examples of fluorine-based surfactants include MEGAFACE F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, and F-554 manufactured by DIC Corporation. , F-556 and F-557, Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited, etc., but are not limited to these. When using a surfactant, the blending amount of the surfactant is preferably 0.01 to 10% by weight based on 100 parts by mass of the resin.

(solvent) The photosensitive resin composition may typically contain a solvent. As a solvent, an organic solvent can be preferably used. Specifically, one or more of a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, a lactone solvent, a carbonate solvent, etc. can be used.

Examples of the solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N- Methylpyrrolidone (NMP), methyl n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone or the like mixture. The usage amount of the solvent is not particularly limited, but it is used in an amount such that the concentration of the non-volatile component becomes, for example, 10 to 70 mass %, preferably 15 to 60 mass %.

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

When the photosensitive resin composition contains a light-shielding agent, its amount can be appropriately set according to the purpose or use. However, from the viewpoint of balancing light-shielding performance and dispersion stability of the light-shielding agent, relative to the non-volatile components of the photosensitive resin composition The total amount (components other than solvent) is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and still more preferably 10 to 50 mass %.

(cross-linking agent) The photosensitive resin composition of this embodiment may contain a crosslinking agent. The cross-linking agent is not particularly limited as long as it is one that can cross-link the polymer P by the action of active chemical species generated from the photopolymerization initiator (one that can chemically bond with the polymer P). The cross-linking agent does not only chemically bond with the polymer, but can also react with each other to form bonds.

The cross-linking agent is, for example, preferably a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylyl group having two or more (meth)acrylyl groups in one molecule. ) acrylic compound (however, the cross-linking agent does not correspond to the aforementioned polymer). From the viewpoint of uniform curability and further improvement in sensitivity, it is preferable to use a crosslinking agent having the same type of crosslinking group (polymerizable double bond) as the crosslinking group (polymerizable double bond) possessed by the polymer. The upper limit of the number of functions (number of polymerizable double bonds) per molecule of the cross-linking agent is not particularly defined, but is, for example, 8 or less, preferably 6 or less.

Specific examples of the crosslinking agent include the following: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and propylene glycol. Di(meth)acrylate, butylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A epoxide di (meth)acrylate (bisphenol A alkylene oxide di(meth)acrylate), bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylol Propane tetra(meth)acrylate, glycerol tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate, dineopenterythritol Hexa(meth)acrylate, ethylene oxide plus trimethylolpropane tri(meth)acrylate, ethylene oxide plus ditrimethylolpropane tetra(meth)acrylate, ethylene oxide Alkane addition to neopenterythritol tetra(meth)acrylate, ethylene oxide addition to dineopenterythritol hexa(meth)acrylate, propylene oxide addition to trimethylolpropane tri(meth)acrylic acid Ester, propylene oxide added to ditrimethylolpropane tetra(meth)acrylate, propylene oxide added to neopentylerythritol tetra(meth)acrylate, propylene oxide added to dineopenterythritol hexa(meth)acrylate Meth)acrylate, ε-caprolactone added to trimethylolpropane tri(meth)acrylate, ε-caprolactone added to ditrimethylolpropane tetra(meth)acrylate, ε-hexanoic acid Polyfunctional (meth)acrylates such as lactone addition to neopenterythritol tetra(meth)acrylate and ε-caprolactone addition to dipenterythritol hexa(meth)acrylate; Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexylene glycol divinyl ether, bisphenol A Alkylene oxide divinyl ether, Bisphenol F Alkylene oxide divinyl ether, Trimethylolpropane trivinyl ether, Ditrimethylolpropane tetravinyl ether, Glycerol trivinyl ether, New Pentaerythritol tetravinyl ether, dineopenterythritol pentavinyl ether, dineopenterythritol hexavinyl ether, ethylene oxide addition trimethylolpropane trivinyl ether, ethylene oxide addition Multifunctional vinyl ethers such as ditrimethylolpropane tetravinyl ether, ethylene oxide added to neopentyl erythritol tetravinyl ether, ethylene oxide added to dineopenterythritol hexavinyl ether; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxy (meth)acrylate Ethyl ester, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-(meth)acrylate Ethyleneoxypentyl ester, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-ethyleneoxymethylphenylmethyl (meth)acrylate Ester, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, etc. containing vinyl ether groups (meth)acrylates; Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexylene glycol diene Propyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether , Glycerol triallyl ether, neopentylerythritol tetraallyl ether, dineopenterythritol pentaallyl ether, dineopenterythritol hexaallyl ether, ethylene oxide added to trihydroxy Methylpropane triallyl ether, ethylene oxide addition to ditrimethylolpropane tetraallyl ether, ethylene oxide addition to neopentaerythritol tetraallyl ether, ethylene oxide addition to di Polyfunctional allyl ethers such as neopentylerythritol hexaallyl ether; Allyl (meth)acrylate and other allyl-containing (meth)acrylates; Tris(acryloxyethyl) isocyanate, tris(methacryloyloxyethyl) isocyanate, alkylene oxide added to tris(acryloxyethyl) isocyanate, alkylene oxide added to tris(methyl) Acryloxyethyl) isocyanate and other polyisocyanates containing polyfunctional (meth)acrylyl groups; Triallyl isocyanate and other cyanuric isocyanates containing multifunctional allyl groups; By using polyfunctional isocyanates such as toxinyl diisocyanate, isophorone diisocyanate, and styryldiisocyanate, and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. Multifunctional amine ester (meth)acrylates obtained by the reaction of (meth)acrylates; Polyfunctional aromatic vinyls such as divinylbenzene.

Among them, preferred are trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, and neopentylerythritol tetra(meth)acrylate. , tetrafunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, and hexafunctional (meth)acrylates such as dineopenterythritol hexa(meth)acrylate.

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

(Other additives) The photosensitive resin composition may contain fillers, binder resins other than the above-mentioned polymers, acid generators, heat resistance improvers, development aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, and antioxidants depending on various purposes or required characteristics. , matting agent, defoaming agent, leveling agent, antistatic agent, dispersant, slip agent, surface modifier, thixotropic agent, thixotropic additive, silane coupling agent, polyvalent phenol compound and other ingredients .

[use] A patterned film can be obtained by forming a film using the photosensitive resin composition and exposing/developing the film to form a pattern. This film is suitable for color filters or black matrices, etc. That is, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. Furthermore, a black matrix can be obtained by forming a pattern using a photosensitive resin composition containing a light-shielding agent. Then, a liquid crystal display device or a solid-state imaging device including a color filter or a black matrix can be manufactured. A typical procedure for forming patterns is explained.

(Formation of photosensitive resin film) For example, a photosensitive resin film is first obtained by applying the above-mentioned photosensitive resin composition on an arbitrary substrate and drying it as necessary.

The substrate on which the composition is coated is not particularly limited. Examples include glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, copper-clad laminates, and the like. The substrate may be an unprocessed substrate or a substrate with electrodes or components formed on the surface. In order to improve the adhesion, surface treatment can be performed.

The coating method of the photosensitive resin composition is not particularly limited. It can be performed by spin coating using a spin coater, spray coating using a spray coater, dipping, printing, roller coating, inkjet method, etc.

Drying of the photosensitive resin composition applied on the substrate is typically performed by heat treatment using a hot plate, hot air, oven, or the like. The heating temperature is usually 80 to 140°C, preferably 90 to 120°C. Moreover, the heating time is usually 30 to 600 seconds, preferably about 30 to 300 seconds.

The film thickness of the photosensitive resin film is not particularly limited and can be appropriately adjusted according to the final pattern to be obtained. It is usually 0.5 to 10 μm, preferably 1 to 5 μm. In addition, the film thickness can be adjusted according to the content of the solvent in the photosensitive resin composition, the coating method, etc.

(exposure) Exposure is typically performed by irradiating active light onto the photosensitive resin film through an appropriate mask.

Examples of active rays include X-rays, electron beams, ultraviolet rays, visible rays, and the like. In terms of wavelength, light of 200 to 500 nm is preferred. From the viewpoint of pattern resolution or operability, the light source is preferably g-rays, h-rays or i-rays of a mercury lamp, and particularly preferably i-rays. In addition, two or more types of light may be mixed and used. As the exposure device, a contact aligner, a mirror projection aligner or a stepper is preferred. The amount of exposure light can be appropriately adjusted according to the amount of photosensitive agent in the photosensitive resin film, and is, for example, about 100 to 500 mJ/cm ² .

Furthermore, after exposure, the photosensitive resin film can be heated again if necessary (post-exposure heating: Post Exposure Bake). The temperature is, for example, 70 to 150°C, preferably 90 to 120°C. Moreover, the time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. By heating after exposure, the reaction caused by the free radicals generated from the photoradical polymerization initiator is promoted, and the hardening reaction is further promoted.

(Develop) By developing the exposed photosensitive resin film with an appropriate developer, a pattern can be obtained, and a substrate having a pattern can be manufactured. Since the photosensitive resin film composed of the photosensitive resin composition containing the polymer solution of this embodiment has excellent adhesion to the substrate, peeling of the pattern can be suppressed during the development step.

In the development step, an appropriate developer may be used and development may be performed using a method such as a dipping method, a puddle method, a spin spray method, or the like. By development, the exposed part (in the case of positive type) or the unexposed part (in the case of negative type) of the photosensitive resin film is elute-removed, and a pattern is obtained. The developer that can be used is not particularly limited. For example, an alkali aqueous solution or an organic solvent can be used.

Specific examples of the alkali aqueous solution include (i) inorganic alkali aqueous solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, and (ii) organic amine aqueous solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine. , (iii) Aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Since the polymer of this embodiment can adjust its alkali solubility and has excellent sensitivity, when a strong alkaline developer such as TMAH (tetramethylammonium hydroxide) solution is used, the pattern after exposure and development can be made into a designed shape. .

Specific examples of the organic solvent 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. For example, water-soluble organic solvents such as methanol and ethanol or surfactants may be added to the developer.

In this embodiment, as the developer, an alkali aqueous solution is preferably used, and tetramethylammonium hydroxide, a sodium carbonate aqueous solution, or a potassium hydroxide aqueous solution is more preferably used. The concentration of the aqueous alkali solution is preferably 0.01 to 10% by mass, more preferably 0.5 to 5% by mass. Through the above steps, a pattern can be obtained/a substrate having a pattern can be manufactured, but various processes can be performed after development.

For example, after development, the pattern and substrate can be cleaned with a rinse solution. Examples of the rinse liquid include distilled water, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether, and the like. One type of these may be used alone, or two or more types may be used in combination.

Moreover, the obtained pattern can be heated and fully hardened. The heating temperature is typically 150 to 400°C, preferably 160 to 300°C, and more preferably 200 to 250°C. The heating time is not particularly limited, but is, for example, in the range of 15 to 300 minutes. This heating treatment can be performed using a heating plate, an oven, a temperature-raising oven capable of setting a temperature program, etc. The ambient gas during the heat treatment may be air or inert gas such as nitrogen or argon. Alternatively, heating may be performed under reduced pressure. An example of the structure of a liquid crystal display device and/or a solid-state imaging element including a color filter and/or a black matrix is schematically shown in FIG. 1 . In addition, a black matrix can be used as a black bank. The following description will be made on a liquid crystal display device and/or a solid-state imaging element including a color filter and a black matrix.

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

The substrate 10 is usually made of a material through which light can pass. For example, in addition to glass, it may also be made of polyester, polycarbonate, polyolefin, polystyrene, cyclic olefin polymer, and the like. The substrate 10 may be subjected to corona discharge treatment, ozone treatment, chemical solution treatment, etc. as necessary. The substrate 10 is preferably made of glass. The black matrix 11 is made of, for example, a cured product of a photosensitive resin composition containing a light-shielding agent.

As the color filter 12, there are usually three colors: red, green, and blue. The color filter 12 is composed of a cured product of a photosensitive resin composition containing a colorant corresponding to each color.

The embodiments of the present invention have been described above. However, these are examples of the present invention, and various configurations other than those described above can also be adopted. Example

Hereinafter, the present invention will be described using Examples and Comparative Examples, but the present invention is not limited to these.

The compounds used in the examples may be represented by the following abbreviations or trade names. ·MAN: Maleic anhydride ·NB: 2-norbornene ·FADB: dibutyl fumarate ·FADE: diethyl fumarate ·FABEH: Fumarate bis(2-ethylhexyl) ·MADB: dibutyl maleate ·PhMI: N-phenylmaleimide ·MEK: Methyl Ethyl Ketone ·GMA: Glycidyl methacrylate ·PEMP: Neopentaerythritol tetrakis (3-mercaptopropionate), a thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemical Co., Ltd.) ·4-HBA: 4-hydroxybutyl acrylate ·A-TMM-3LM-N: A mixture of the following two compounds, the amount of the compound on the left in the mixture measured by gas chromatography is approximately 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

＜Synthesis of raw material polymer＞ (Synthesis of raw material polymer 1) Add 602.56g of 75% toluene solution of 2-norbornene (converted to 2-norbornene, 451.92g, 4.8mol) and maleic anhydride (MAN, 470.69) into a reaction vessel equipped with a stirrer, cooling tube and dropping funnel. g, 4.8 mol) and 2281.74 g of methyl ethyl ketone (MEK), and stirred/dissolved. Next, the dissolved oxygen in the system was removed by bubbling nitrogen, and then the temperature was raised. When the internal temperature reached 80°C, 2,2'-azobisisobutyric acid dimethyl ester (Wako Pure Chemical) was added over an hour. Manufactured by Industries, Ltd., trade name: V-601, 44.21g, 0.19mol) and PEMP (93.82g, 0.19mol) dissolved in MEK193.4g. Thereafter, the reaction was further carried out at 80° C. for 7 hours. Next, 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 further washed with 3686.4 g of methanol, and then vacuum dried at a temperature of 120° C., thereby obtaining a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The polymer (raw material polymer 1) 910.1g. The obtained polymer raw material 1 was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 3,500, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.62.

(Confirmation of the thioether structure contained in the raw material polymer 1) By ¹³ C-NMR measurement of the PEMP monomer represented by the chemical formula, peak a derived from carbon a was confirmed at around 19.0 ppm and around 62.0 ppm. To peak b from carbon b.

In the ¹³ C-NMR measurement of the raw material polymer 1 synthesized using PEMP, the appearance of peak b derived from carbon b was confirmed around 62.0 ppm. In the GPC measurement of the reaction solution, no peak of the PEMP monomer was observed, and unreacted PEMP did not remain. This confirmed that PEMP was absorbed into the raw material polymer 1.

Furthermore, in the ¹³ C-NMR measurement of the raw material polymer 1, the peak a derived from the carbon a was not confirmed, and instead, the peak c corresponding to the thioether (RS-R') appeared near 28 ppm. The integrated value of peak c is approximately twice the integrated value of peak b. Therefore, the base polymer 1 has a skeleton having a thioether group as described below, and the thiol group has disappeared.

The conditions for ¹³ C-NMR measurement are as follows. (Test conditions) A measurement sample is prepared by adding a measurement solvent to a weighed sample to adjust the concentration, and then injecting a prescribed amount into a sample tube for NMR measurement. ·Measurement device: JNM-ECA400 superconducting FT-NMR device of JEOL Ltd. ·Resonance frequency: 100.53MHz ·Measurement core: ¹³ C ·Measurement method: NNE measurement (Inverse Gate Decoupling Method) · Pulse width: 3.83μsec ·Pulse repetition waiting time: 30s ·Cumulative number of times: 4096 times ·Measurement temperature: room temperature ·Measurement solvent: DMSO-d ₆ (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, and the presence of sulfur element in the polymer was confirmed. In addition, GPC measurement of the reaction solution before methanol was added dropwise also confirmed that the peak derived from PEMP disappeared and PEMP was absorbed into the raw material polymer 1.

Elemental analysis was performed, and the result was that the sulfur content in the raw material polymer 1 was 2.4 wt%.

(Synthesis of raw material polymer 2) Add 602.56g of 75% toluene solution of 2-norbornene (451.92g as NB, 4.8mol) and maleic anhydride (MA, 470.69g, 4.8mol) into a reaction vessel equipped with a stirrer, cooling tube and dropping funnel. ) and 2238.50g of methyl ethyl ketone (MEK), and stirred/dissolved. Next, the dissolved oxygen in the system was removed by bubbling nitrogen, and then the temperature was raised. When the internal temperature reached 80°C, 2,2'-azobisisobutyric acid dimethyl ester (dimethyl azobisisobutyrate) was added over 1 hour. Manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601, 44.21g, 0.19mol) and neopentylerythritol tetrakis(3-mercaptopropionate) (PEMP, 140.73g, 0.29mol) dissolved in MEK189.74g The resulting solution. Thereafter, the reaction was further carried out at 80° C. for 7 hours. Next, 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 further washed with 3686.4 g of methanol, and then vacuum dried at a temperature of 120° C., thereby obtaining a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The polymer (raw material polymer 2) 908.1g. The obtained polymer raw material 2 was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 2,700, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.57.

The amount of sulfur in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur element was present in the polymer. In addition, in the GPC measurement of the reaction solution before methanol was added dropwise, it was confirmed that the peak derived from PEMP disappeared and PEMP was absorbed into the polymer.

(Synthesis of raw material polymer 3) Add 50.21g of 75% toluene solution of 2-norbornene (2-norbornene converted to 37.66g, 0.400 mol) and maleic anhydride (MAN) into a reaction vessel equipped with a stirrer, cooling tube and dropping funnel. , 78.45g, 0.800 mol), dibutyl fumarate (FADB) 91.32g (0.400 mol), methyl ethyl ketone (MEK) 540.04g, and stirred/dissolved. Next, the dissolved oxygen in the system was removed by bubbling nitrogen, and then the temperature was raised. When the internal temperature reached 80°C, 2,2'-azobisisobutyric acid dimethyl ester (Wako Pure Chemical) was added over an hour. Manufactured by Industries, Ltd., trade name: V-601, 7.37g, 0.032mol) and PEMP (15.64g, 0.032mol) dissolved in MEK45.78g. Thereafter, the reaction was further carried out at 80° C. for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 3213.2 g of methanol to precipitate a white solid. The obtained white solid was further washed with 803.3 g of methanol, and then vacuum dried at a temperature of 120° C., thereby obtaining a structural unit derived from 2-norbornene and a structural unit derived from fumaric anhydride. and 67.7 g of a polymer (raw material polymer 3) derived from structural units of maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 2,300, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.52.

The amount of sulfur in the obtained raw material polymer 3 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur element was present in the raw material polymer 3 . In addition, in the GPC measurement of the reaction solution before methanol was added dropwise, it was confirmed that the peak derived from PEMP disappeared and PEMP was absorbed into the polymer.

(Synthesis of raw material polymer 4) Add 112.98g of 75% toluene solution of 2-norbornene (2-norbornene converted to 84.75g, 0.900mol) and maleic anhydride (MAN, 88.25g, 0.900mol), 102.73g dibutyl fumarate (0.450mol) and methyl ethyl ketone (MEK) 179.12g, and stirred/dissolved. Next, the dissolved oxygen in the system was removed by bubbling nitrogen, and then the temperature was raised. When the internal temperature reached 70°C, 2,2'-azobisisobutyric acid dimethyl ester (Wako Pure Chemical) was added over an hour. Manufactured by Industries, Ltd., trade name: V-601, 10.36g, 0.045mol) and PEMP (32.98g, 0.0675mol) dissolved in MEK76.77g. Furthermore, the temperature was raised to 80°C, and after the temperature was raised, the reaction was carried out 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 a temperature of 120° C., thereby obtaining a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The polymer (raw material polymer 4) 154.2g. The obtained polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 2,800, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.54.

[Structural analysis of raw material polymer 4] In the synthesis of the raw material polymer 4, when the reaction starts, the monomer and PEMP are dissolved in the solvent, and then the reaction proceeds to generate the polymer. The reaction solution and the obtained polymer were analyzed respectively, and the following results were obtained.

(a) Analysis of reaction solution In the GPC measurement of the reaction solution before reprecipitation purification, no peak of the PEMP monomer was observed. That is, it was confirmed that PEMP did not remain in the reaction solution. Furthermore, in the GC (gas chromatography) measurement of the reaction solution before reprecipitation purification, it was confirmed that the amount of norbornene monomer and dibutyl fumarate in the reaction solution after the reaction was lower than before the reaction. The peaks of the monomer and the maleic anhydride monomer decrease, and the norbornene monomer, the dibutyl fumarate monomer, and the maleic anhydride react to form a polymer.

(b) Analysis of polymers In the GPC measurement of the polymer after reprecipitation and purification, no peaks of the PEMP monomer, norbornene monomer, dibutyl fumarate monomer, and maleic anhydride monomer were observed. That is, it was confirmed that PEMP, norbornene monomer, dibutyl fumarate monomer, and maleic anhydride monomer did not remain in the polymer.

Regarding the raw material polymer 4, the ratio of the structure derived from each monomer actually introduced into the raw polymer calculated by ¹³ C-NMR is norbornene: dibutyl fumarate: maleic anhydride =48.0%: 9.0%: 46.7%. The amount of PEMP actually introduced into the raw polymer is 3.4 mol% relative to the total amount of each monomer.

The amount of sulfur in the obtained raw material polymer 4 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur element was present in the raw material polymer 4 . In addition, in the GPC measurement of the reaction solution before methanol was added dropwise, it was confirmed that the peak derived from PEMP disappeared and PEMP was absorbed into the polymer.

(Confirmation of the structure of the raw material polymer 4) The structure of the structural unit derived from PEMP and dibutyl fumarate (FADB) in the raw material polymer 4 was calculated through integrated value analysis of ¹³ C-NMR unit (structural unit of formula (AD)), structural unit derived from maleic anhydride (MAN) (structural unit of formula (MA)) and structure derived from norbornene (NB) (formula (NB) structural unit) (Molar fraction, Mol%). ^{The 13} C-NMR spectrum is shown in Figure 2. The chemical shifts of the ¹³ C-NMR spectrum were assigned to each structural unit as follows, and the corresponding integral values were measured. ·K of PEPM (4C): 62.0～64.0ppm ·Alkyl terminal of FADB (2C): 13.0～15.0ppm ·G of maleic anhydride ester (2C) + PEMP (4C): 170.0～174.7ppm ·Syn. Butenedioate (2C) + FADB ester (2C): 174.7 to 178.0ppm Alkyl chain: 20 to 60ppm DMSO: around 40ppm Norbornene (7C) = Alkyl chain-DMSO-PEMP (9C , h+i+j)-maleic anhydride (2C)-maleic acid (2C)-FADB (6C) Here, from the maleic anhydride actually introduced into the raw polymer The structural ratio is calculated including the structure of maleic acid ring-opened by maleic anhydride in addition to the structural unit of formula (MA).

(Synthesis of raw material polymer 5) Except that 51.73 g (0.225 mol) of dibutyl fumarate (FADB) was used, in the same manner as the raw material polymer 4, a structural unit derived from 2-norbornene was obtained. 111.5 g of a polymer containing structural units of dibutyl fumarate and structural units derived from maleic anhydride (raw material polymer 5). The obtained polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 3,000, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.69.

The amount of sulfur in the obtained raw material polymer 5 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur element was present in the raw material polymer 5 . In addition, in the GPC measurement of the reaction solution before methanol was added dropwise, it was confirmed that the peak derived from PEMP disappeared and PEMP was absorbed into the polymer.

(Synthesis of raw material polymer 6) Except that 77.48 g (0.450 mol) of diethyl fumarate (FADE) was used instead of dibutyl fumarate (FADB), the polymer was obtained in the same manner as the raw material polymer 4. 148.1 g of a polymer containing structural units derived from 2-norbornene, structural units derived from diethyl fumarate, and structural units derived from maleic anhydride (raw material polymer 6). The obtained polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 2,600, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.52.

The amount of sulfur in the obtained raw material polymer 6 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur element was present in the raw material polymer 6 . In addition, in the GPC measurement of the reaction solution before methanol was added dropwise, it was confirmed that the peak derived from PEMP disappeared and PEMP was absorbed into the polymer.

(Synthesis of raw material polymer 7) Instead of dibutyl fumarate (FADB), 153.22 g (0.450 mol) of bis(2-ethylhexyl) fumarate (FABEH) was used. In addition, 4 In the same manner, a polymer having structural units derived from 2-norbornene, structural units derived from bis(2-ethylhexyl fumarate), and structural units derived from maleic anhydride was obtained. (Raw material polymer 7) 169.1g. The obtained polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 2,900, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.59.

The amount of sulfur in the obtained raw material polymer 7 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur element was present in the raw material polymer 7 . In addition, in the GPC measurement of the reaction solution before methanol was added dropwise, it was confirmed that the peak derived from PEMP disappeared and PEMP was absorbed into the polymer.

(Synthesis of raw material polymer 8) Except that 205.46 g (0.900 mol) of dibutyl maleate (MADB) was used instead of dibutyl fumarate (FADB), a polymer having the properties of raw material polymer 4 was obtained. 155.1 g of a polymer containing structural units derived from 2-norbornene, structural units derived from dibutyl maleate, and structural units derived from maleic anhydride (raw material polymer 8). The obtained polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 2,400, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.45.

The amount of sulfur in the obtained raw material polymer 8 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur element was present in the raw material polymer 8 . In addition, in the GPC measurement of the reaction solution before methanol was added dropwise, it was confirmed that the peak derived from PEMP disappeared and PEMP was absorbed into the polymer.

(Synthesis of raw material polymer 9) Add 112.98g of 75% toluene solution of 2-norbornene (2-norbornene converted to 84.75g, 0.900mol) and maleic anhydride (MAN, 70.60g, 0.720mol), 82.18g dibutyl fumarate (0.360mol) and 157.78g methyl ethyl ketone (MEK), and stirred/dissolved. Next, the dissolved oxygen in the system was removed by bubbling nitrogen, and then the temperature was raised. When the internal temperature reached 70°C, 2,2'-azobisisobutyric acid dimethyl ester (Wako Pure Chemical) was added over an hour. Manufactured by Industries, Ltd., trade name: V-601, 9.12g, 0.040mol) and PEMP (19.35g, 0.040mol) dissolved in MEK 67.62g. Furthermore, the temperature was raised to 80°C, and after the temperature was raised, the reaction was carried out 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 a temperature of 120° C., thereby obtaining a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The polymer (raw material polymer 9) 161.2g. The obtained polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 3,100, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.81.

(Synthesis of raw material polymer 10) Add 251.07g of 75% toluene solution of 2-norbornene (2-norbornene converted to 188.33g, 2.0 mol) and maleic anhydride (MAN) into a reaction vessel equipped with a stirrer, cooling tube and dropping funnel. , 88.25g, 0.900 mol), dibutyl fumarate 456.58g (2.0 mol), N-phenylmaleimide 17.32g (0.100 mol), methyl ethyl ketone ( MEK) 373.94g and stirred/dissolved. Next, the dissolved oxygen in the system was removed by bubbling nitrogen, and then the temperature was raised. When the internal temperature reached 70°C, 2,2'-azobisisobutyric acid dimethyl ester (Wako Pure Chemical) was added over an hour. Manufactured by Industries, Ltd., trade name: V-601, 23.38g, 0.102mol) and PEMP (71.83g, 0.147mol) dissolved in MEK 201.35g. Furthermore, the temperature was raised to 80°C, and after the temperature was raised, the reaction was carried out at 80°C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 11869.0 g of 2-propanol, thereby precipitating a white solid. The obtained white solid was further washed with 5934.0 g of 2-propanol, and then vacuum dried at a temperature of 120°C to obtain fumaric acid-derived structural units having a structural unit derived from 2-norbornene. 324.7 g of a polymer containing structural units of dibutyl ester, structural units derived from N-phenylmaleimide, and structural units derived from maleic anhydride (raw material polymer 10). The obtained polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 2,600, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.90.

The amount of sulfur in the obtained raw material polymer 10 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur element was present in the raw material polymer 10 . In addition, in the GPC measurement of the reaction solution before methanol was added dropwise, it was confirmed that the peak derived from PEMP disappeared and PEMP was absorbed into the polymer.

(raw polymer 11) Add 188.3g of 75% toluene solution of 2-norbornene (2-norbornene converted to 141.25g, 1.50mol) and maleic anhydride (MAN, 88.25g, 0.900mol), dibutyl fumarate 273.95 (1.20mol) and methyl ethyl ketone (MEK) 432.90g, and stirred/dissolved. Next, the dissolved oxygen in the system was removed by bubbling nitrogen, and then the temperature was raised. When the internal temperature reached 80°C, 2,2'-azobisisobutyric acid dimethyl ester (Wako Pure Chemical) was added over an hour. Industries, Ltd., trade name: V-601, 17.08g, 0.074mol) is a solution dissolved in MEK 48.10g. Furthermore, it was allowed to react for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 6057.0 g of methanol to precipitate a white solid. The obtained white solid was further washed with 1,652.0 g of methanol, and then vacuum dried at a temperature of 120° C., thereby obtaining a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The polymer (raw material polymer 11) 244.1g. The obtained polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 3,400, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.48.

For raw material polymers 3 to 11, the amount of each monomer in the reaction solution before and after the reaction was measured by gas chromatography (GC) measurement to calculate the consumption of each monomer, thereby calculating the amount introduced into the raw material polymer. The ratio of each monomer. The following Table 1 shows the input ratio of the monomers used in the synthesis of the base polymer, the ratio of the monomers introduced into the base polymer, the weight average molecular weight (Mw) and the polydispersity of the base polymer. (Mw/Mn). The measurement conditions for gas chromatography measurements are as follows. ·GC device: GC-2030 (SHIMADZU CORPORATION) ·Carrier gas: N ₂ ·Detector: Hydrogen flame ionization (FID) detector, FID temperature: 300℃ ·Column: SH-RXi-1HT, inner diameter 0.25, Length 30m, film thickness 0.25μm (Shimadzu GLC Ltd.) ·Vaporization chamber temperature: 210℃ ·Column flow rate: 0.64mL/min ·Column heating conditions: 50℃ maintained for 5min, heated to 300℃ at 20℃/min, Keep at 300℃ for 10min

[Table 1] Table 1 Raw material polymer No. Amount of PEMP in base polymer (vs monomer) Type of monomer used Input monomer ratio (mol ratio) Monomer introduction ratio (mol ratio) Weight average molecular weight (Mw) Polydispersity (Mw/Mn) Softening point (℃) (TMA) Melting point (℃) (Tg-DTA) Raw polymer 1 2mol% NB/MAN 50/50 - 3,500 1.62 165 225 Raw polymer 2 3mol% NB/MAN 50/50 - 2,700 1.57 146 182 Raw polymer 3 2mol% NB/FADB/MAN 25/25/50 50/10/40 2,300 1.52 97 121 Raw polymer 4 3mol% NB/FADB/MAN 40/20/40 48/12/38 2,800 1.54 105 119 Raw polymer 5 3mol% NB/FADB/MAN 40/10/40 48/9/43 3,000 1.69 110 127 Raw polymer 6 3mol% NB/FADE/MAN 40/20/40 49/11/40 2,600 1.52 117 138 Raw polymer 7 3mol% NB/FABEH/MAN 40/20/40 51/8/41 2,900 1.59 80 108 Raw polymer 8 3mol% NB/MADB/MAN 40/40/40 53/5/42 2,400 1.45 112 132 Raw polymer 9 2mol% NB/MAN/FADB 50/40/20 52/42/6 3,100 1.81 115 138 Raw polymer 10 3mol% NB/MAN/FADB/PhMI 50/22.5/50/2.5 50/24/23/3 2,600 1.90 55 76 Raw polymer 11 - NB/MAN/FADB 50/30/40 47/33/20 3,400 1.48 124 146

＜Synthesis of Polymer P＞ Polymer P was produced using the following method.

(Preparation Example 1) A polymer P1 was produced in which the MA unit of the raw material polymer 1 was ring-opened with a monofunctional (meth)acrylic acid compound. The details are explained below. First, 18.44 g of MEK was added to 10.00 g of the raw material polymer 1 (calculated from the input amount of the raw material polymer 1 and 0.052 mol in terms of MA) to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to the solution, and then 3.00 g (0.030 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 6 hours to prepare a reaction solution. The obtained reaction solution was diluted with MEK and treated with a citric acid aqueous solution, thereby removing the aqueous phase from the reaction solution. Thereafter, the polymer was purified by the reprecipitation method described below. ·Re-precipitation method: Use excess water to reprecipitate the polymer. The operation of washing the polymer powder obtained by reprecipitation with excess water was repeated twice. The reaction product obtained was dried at 40°C for 12 hours. Through the above, 8.7 g of the polymer P1 in which the structural unit derived from maleic anhydride in the raw material polymer 1 was ring-opened with 4-HBA was obtained. GPC measurement was performed on the obtained polymer P1, and the weight average molecular weight and polydispersity of the polymer P1 were measured. The results are shown in Table 2. Furthermore, GPC measurement of the polymer P1 confirmed the disappearance of the peak of the monofunctional (meth)acrylic acid compound used. This confirmed that the obtained polymer P1 did not contain unreacted monofunctional (meth)acrylic acid compound.

(Preparation Example 2) A polymer P2 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound and water was produced. The details are explained below. First, 99.93 g of MEK was added to 60.00 g of the raw material polymer 1 (0.312 mol calculated from the input amount of the raw material polymer 1 and converted to MA) to prepare a solution. Next, 77.49 g of A-TMM-3LM-N was added to the solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 2 hours. Thereafter, 56.27 g (0.390 mol) of 4-HBA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours to prepare a reaction solution. Next, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70° C. for 2 hours. The obtained reaction solution was diluted with MEK and treated with a citric acid aqueous solution, thereby removing the aqueous phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the following procedure, and then solvent replacement was performed. ·Liquid-liquid extraction: The reaction solution was diluted with MEK, and then water was added for treatment to remove the aqueous phase from the reaction solution. The same operation was further performed once. ·Solvent replacement: The solvent was removed from the obtained reaction mixture using a rotary evaporator under reduced pressure and at 50°C. It was confirmed that the solid content concentration of the polymer solution was 27±2% by mass as measured by a heating drying moisture meter, and the operation of removing the solvent was discontinued. Thereafter, PGMEA was added so that the solid content concentration became 18% by mass, and the mixture was mixed until uniform. The same operation was repeated two more times: the solvent was removed under reduced pressure at 50°C, and the solid content concentration was adjusted to 27±2 mass% by measurement with a heating drying moisture meter. , further add PGMEA so that the solid content concentration becomes 18% by mass, and mix until uniform. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration became 30±3% by mass, and the mixture was stirred until it became uniform. Through the above operation, the solvent used in the reaction was removed and the solvent was replaced with PGMEA. Thereafter, further purification was carried out by the following procedure. • The polymer was reprecipitated with excess toluene. ·The operation of washing the polymer powder obtained by reprecipitation with excess toluene was repeated twice. ·The polymer powder washed twice with excess water was washed three times. ·The reaction product obtained was dried at 40°C for 12 hours. Through the above, a polymer P2 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound and water was produced. GPC measurement was performed on the obtained polymer P2, and the weight average molecular weight and polydispersity of the polymer P2 were measured. The results are shown in Table 2. Furthermore, GPC measurement of the polymer P2 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P2 contained neither an unreacted polyfunctional (meth)acrylic compound nor a monofunctional (meth)acrylic compound. Furthermore, through ¹³ C-NMR measurement, it was 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.

(Preparation Example 3) A resin mixture (polymer solution P3) containing polymer P3 obtained by ring-opening the MA unit of the raw material polymer 1 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound, and water was produced. The details are explained below. First, 99.93 g of MEK was added to 60.00 g of the raw material polymer 1 (0.312 mol calculated from the input amount of the raw material polymer 1 and converted to MA) to prepare a solution. Next, 77.49 g of A-TMM-3LM-N was added to the solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 2 hours. Thereafter, 56.27 g (0.390 mol) of 4-HBA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours to prepare a reaction solution. Next, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70° C. for 2 hours. The obtained reaction solution was diluted with MEK, and treated with a formic acid aqueous solution and a citric acid aqueous solution, thereby removing the aqueous phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the following procedure, and then solvent replacement was performed. ·Liquid-liquid extraction: The reaction solution was diluted with MEK, and then water was added for treatment to remove the aqueous phase from the reaction solution. The same operation was further performed once. ·Solvent replacement: The solvent was removed from the obtained reaction mixture using a rotary evaporator under reduced pressure and at 50°C. It was confirmed that the solid content concentration of the polymer solution was 27±2% by mass as measured by a heating drying moisture meter, and the operation of removing the solvent was discontinued. Thereafter, PGMEA was added so that the solid content concentration became 18% by mass, and the mixture was mixed until uniform. The same operation was repeated two more times: the solvent was removed under reduced pressure at 50°C, and the solid content concentration was adjusted to 27±2 mass% by measurement with a heating drying moisture meter. , further add PGMEA so that the solid content concentration becomes 18% by mass, and mix until uniform. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration became 30±3% by mass, and the mixture was stirred until it became uniform. Through the above operation, the solvent used in the reaction was removed and the solvent was replaced with PGMEA.

Through the above, a polymer P3 containing structural units derived from maleic anhydride in the base polymer 1 ring-opened with A-TMM-3LM-N, 4-HBA and water, and remaining (free) A- was obtained. Resin mixture of TMM-3LM-N and residual (free) 4-HBA (polymer solution P3). The obtained polymer solution P3 was analyzed by gel permeation chromatography, and the amounts of the polymer P3, the free multifunctional (meth)acrylic acid compound, and the free monofunctional (meth)acrylic acid compound contained in the solution were measured. and the weight average molecular weight and polydispersity of polymer P3. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P3 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express. In addition, the measurement conditions of gel permeation chromatography are as follows. ・As a GPC measurement device, TOSOH CORPORATION's HLC-8320GPC EcoSEC was used. The column temperature was set to 40.0°C, and the pump flow rate was set to 0.350 mL/min. ·Peak position (hold time) Polymer P3: Peak detected 20 minutes ago (peak with shorter retention time and larger molecular weight than A-TMM-3LM-N and 4-HBA) A-TMM-3LM-N: Total of 2 peaks: 20.0 to 20.6 points and 20.6 to 21.5 points 4-HBA: 21.7～22.4 points ·Measurement conditions: Analysis was performed using a differential refractive index detector (RI detector).

(Preparation Example 4) In place of the raw polymer 1, 60.00 g of the raw polymer 2 (0.312 mol calculated from the input amount of the raw polymer 2 and converted to MA) was used in the same manner as in Preparation Example 3. A resin mixture of polymer P4 (polymer solution P4) obtained by ring-opening the MA unit of raw material polymer 2 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound and water.

Under the same conditions as Preparation Example 3, the obtained polymer solution P4 was analyzed by gel permeation chromatography to measure the polymer P4, free polyfunctional (meth)acrylic acid compound and free monomer contained in the solution. The amount of functional (meth)acrylic compounds and the weight average molecular weight and polydispersity of polymer P4. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P4 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 5) Except for using 116.24 g of A-TMM-3LM-N, in the same manner as in Preparation Example 4, a preparation containing a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound and a monofunctional (meth)acrylic acid compound were used as the MA unit of the raw material polymer 2. A resin mixture (polymer solution P5) of polymer P5 obtained by ring-opening of an acrylic compound and water.

Under the same conditions as Preparation Example 3, the obtained polymer solution P5 was analyzed by gel permeation chromatography to measure the polymer P5, free polyfunctional (meth)acrylic acid compound and free monomer contained in the solution. The amount of functional (meth)acrylic compounds and the weight average molecular weight and polydispersity of polymer P5. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P5 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 6) In place of the raw polymer 1, 10.00 g of the raw polymer 4 was used (the mole calculated from the composition ratio calculated based on the GC measurement of the raw polymer 4 and converted to MA was 0.034 mol). , polymer P6 obtained by ring-opening the MA unit of the raw material polymer 4 with a monofunctional (meth)acrylic acid compound was produced in the same manner as in Preparation Example 1. GPC measurement was performed on the obtained polymer P6, and the weight average molecular weight and polydispersity of the polymer P6 were measured. The results are shown in Table 2. Furthermore, GPC measurement of polymer P6 confirmed the disappearance of the peak of the monofunctional (meth)acrylic acid compound used. Through this, it was confirmed that the unreacted monofunctional (meth)acrylic acid compound was not included in the obtained polymer P6. Furthermore, through ¹³ C-NMR measurement, it was confirmed that polymer P6 has a structure in which the structural unit derived from maleic anhydride is ring-opened with 4-HBA.

(Preparation Example 7) Except for using 60.00 g of the raw polymer 3 instead of the raw polymer 1 (the mole calculated from the composition ratio calculated based on the GC measurement of the raw polymer 3 and converted to MA is 0.220 mol), the same procedures as those in the Preparation Examples were used. 3. In the same manner, a resin mixture (polymer solution) containing polymer P7 obtained by ring-opening the MA unit of raw material polymer 3 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound, and water was produced. P7). Under the same conditions as Preparation Example 3, the polymer solution P7 obtained was analyzed by gel permeation chromatography to measure the polymer P7 and the free polyfunctional (meth)acrylic acid compound contained in the polymer solution P7. and the amount of free monofunctional (meth)acrylic acid compounds as well as the weight average molecular weight and polydispersity of polymer P11. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P7 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 8) In place of the base polymer 1, 60.00 g of the base polymer 4 was used (the mole calculated from the composition ratio calculated based on the GC measurement of the base polymer 4 and converted to MA was 0.204 mol). , in the same manner as in Preparation Example 2, a polymer P8 in which the MA unit of the raw material polymer 4 was ring-opened with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound and water was produced. GPC measurement was performed on the obtained polymer P8, and the weight average molecular weight and polydispersity of the polymer P8 were measured. The results are shown in Table 2. Furthermore, GPC measurement of polymer P8 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. From this, it was confirmed that the obtained polymer P8 contained neither an unreacted polyfunctional (meth)acrylic compound nor a monofunctional (meth)acrylic compound. Furthermore, through ¹³ C-NMR measurement, it was confirmed that polymer P8 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 9) Except for using 60.00 g of the base polymer 4 instead of the base polymer 2 (the mole calculated from the composition ratio calculated based on the GC measurement of the base polymer 4 and converted to MA was 0.204 mol), the same procedures as those in the Preparation Examples were used. 4 In the same manner, a resin mixture (polymer solution) containing polymer P9 obtained by ring-opening the MA unit of raw material polymer 4 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound, and water was produced. P9). Under the same conditions as Preparation Example 3, the obtained polymer solution P9 was analyzed by gel permeation chromatography to measure the polymer P9, free polyfunctional (meth)acrylic acid compound and free monomer contained in the solution. The amount of functional (meth)acrylic compounds and the weight average molecular weight and polydispersity of polymer P9. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P9 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 10) Except for using 60.00 g of the base polymer 4 instead of the base polymer 2 (the mole calculated from the composition ratio calculated based on the GC measurement of the base polymer 4 and converted to MA was 0.204 mol), the same procedures as those in the Preparation Examples were used. 5 In the same manner, a resin mixture (polymer solution) containing polymer P10 obtained by ring-opening the MA unit of raw material polymer 4 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound, and water was produced. P10). Under the same conditions as Preparation Example 5, the obtained polymer solution P10 was analyzed by gel permeation chromatography to measure the polymer P10, free polyfunctional (meth)acrylic acid compound and free monomer contained in the solution. The amount of functional (meth)acrylic compounds and the weight average molecular weight and polydispersity of polymer P10. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P10 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 11) Except for using 60.00 g of the base polymer 5 instead of the base polymer 3 (the mole calculated from the composition ratio calculated based on the GC measurement of the base polymer 5 and converted to MA was 0.239 mol), the same procedures as those in the Preparation Examples were used. 7 In the same manner, a resin mixture (polymer solution) containing polymer P11 obtained by ring-opening the MA unit of raw polymer 5 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound, and water was produced. P11). Under the same conditions as Preparation Example 3, the obtained polymer solution P11 was analyzed by gel permeation chromatography to measure the polymer P11, free polyfunctional (meth)acrylic acid compound and free monomer contained in the solution. The amount of functional (meth)acrylic compounds and the weight average molecular weight and polydispersity of polymer P11. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P11 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 12) In place of the base polymer 4, 60.00 g of the base polymer 5 was used (the mole calculated from the composition ratio calculated based on the GC measurement of the base polymer 5 and converted to MA was 0.239 mol). , in the same manner as in Preparation Example 8, a polymer P12 in which the MA unit of the raw material polymer 5 was ring-opened with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound and water was produced. GPC measurement was performed on the obtained polymer P12, and the weight average molecular weight and polydispersity of the polymer P12 were measured. The results are shown in Table 2. Furthermore, GPC measurement of polymer P12 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. From this, it was confirmed that the obtained polymer P8 contained neither an unreacted polyfunctional (meth)acrylic compound nor a monofunctional (meth)acrylic compound. Furthermore, through ¹³ C-NMR measurement, it was confirmed that polymer P12 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 13) Except for using 60.00 g of the raw polymer 6 instead of the raw polymer 3 (the mole calculated from the composition ratio calculated based on the GC measurement of the raw polymer 6 and converted to MA is 0.230 mol), the same procedures as those in the Preparation Examples were used. 7 In the same manner, a resin mixture (polymer solution) containing polymer P13 obtained by ring-opening the MA unit of raw material polymer 6 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound, and water was produced. P13). Under the same conditions as Preparation Example 3, the obtained polymer solution P13 was analyzed by gel permeation chromatography to measure the polymer P13, free polyfunctional (meth)acrylic acid compound and free monomer contained in the solution. The amount of functional (meth)acrylic compounds and the weight average molecular weight and polydispersity of polymer P13. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P13 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 14) In place of the base polymer 4, 60.00 g of the base polymer 6 was used (the mole calculated from the composition ratio calculated based on the GC measurement of the base polymer 6 and converted to MA was 0.230 mol). , in the same manner as in Preparation Example 8, a polymer P14 in which the MA unit of the raw material polymer 6 was ring-opened with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound and water was produced. GPC measurement was performed on the obtained polymer P14, and the weight average molecular weight and polydispersity of the polymer P14 were measured. The results are shown in Table 2. Furthermore, GPC measurement of polymer P14 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. From this, it was confirmed that the obtained polymer P8 contained neither an unreacted polyfunctional (meth)acrylic compound nor a monofunctional (meth)acrylic compound. Furthermore, through ¹³ C-NMR measurement, it was confirmed that polymer P14 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 15) Except that 60.00 g of raw polymer 7 was used instead of raw polymer 3 (moles calculated from the composition ratio calculated based on GC measurement of raw polymer 7 and converted to MA was 0.213 mol), the same procedures were used as in the preparation examples. 7. In the same manner, a resin mixture (polymer solution) containing polymer P15 obtained by ring-opening the MA unit of raw material polymer 7 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound, and water was produced. P15). Under the same conditions as Preparation Example 3, the obtained polymer solution P15 was analyzed by gel permeation chromatography to measure the polymer P15, free polyfunctional (meth)acrylic acid compound and free monomer contained in the solution. The amount of functional (meth)acrylic compounds and the weight average molecular weight and polydispersity of polymer P15. The results are shown in Table 2. Furthermore, the amount of free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of polymer P15 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 16) In place of the base polymer 4, 60.00 g of the base polymer 7 was used (the mole calculated from the composition ratio calculated based on the GC measurement of the base polymer 7 and converted to MA was 0.213 mol). , in the same manner as in Preparation Example 8, a polymer P16 in which the MA unit of the raw material polymer 7 was ring-opened with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound and water was produced. GPC measurement was performed on the obtained polymer P16, and the weight average molecular weight and polydispersity of the polymer P14 were measured. The results are shown in Table 2. Furthermore, GPC measurement of polymer P16 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. From this, it was confirmed that the obtained polymer P8 contained neither an unreacted polyfunctional (meth)acrylic compound nor a monofunctional (meth)acrylic compound. Furthermore, through ¹³ C-NMR measurement, it was 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.

(Preparation Example 17) In place of the base polymer 3, 60.00 g of the base polymer 8 was used (the mole calculated from the composition ratio calculated based on the GC measurement of the base polymer 8 and converted to MA was 0.246 mol). Except for this, the same procedure as in the preparation example was used. 7. In the same manner, a resin mixture (polymer solution) containing the polymer P17 obtained by ring-opening the MA unit of the raw material polymer 8 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound, and water was produced. P17). Under the same conditions as Preparation Example 3, the obtained polymer solution P17 was analyzed by gel permeation chromatography to measure the polymer P17, free polyfunctional (meth)acrylic acid compound and free monomer contained in the solution. The amount of functional (meth)acrylic compounds and the weight average molecular weight and polydispersity of polymer P17. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P17 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 18) In place of the base polymer 4, 60.00 g of the base polymer 8 was used (the mole calculated from the composition ratio calculated based on the GC measurement of the base polymer 8 and converted to MA was 0.246 mol). , in the same manner as in Preparation Example 8, a polymer P18 in which the MA unit of the raw material polymer 8 was ring-opened with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound and water was produced. GPC measurement was performed on the obtained polymer P18, and the weight average molecular weight and polydispersity of the polymer P18 were measured. The results are shown in Table 2. Furthermore, GPC measurement of polymer P18 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. From this, it was confirmed that the obtained polymer P8 contained neither an unreacted polyfunctional (meth)acrylic compound nor a monofunctional (meth)acrylic compound. Furthermore, through ¹³ C-NMR measurement, it was 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.

(Preparation Example 19) A resin mixture (polymer solution P19) containing polymer P19 obtained by ring-opening the MA unit of the raw material polymer 3 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound, and water was produced. The details are explained below. First, 99.93 g of MEK was added to 60.00 g of the raw material polymer 3 (calculated from the input amount of the raw material polymer 3 and converted to 0.220 mol in terms of MA) to prepare a solution. Next, 77.49 g of A-TMM-3LM-N was added to the solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 2 hours. Thereafter, 56.27 g (0.390 mol) of 4-HBA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours to prepare a reaction solution. Next, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70° C. for 2 hours. The obtained reaction solution was diluted with MEK, and treated with a formic acid aqueous solution and a citric acid aqueous solution, thereby removing the aqueous phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the following procedure, and then solvent replacement was performed. ·Liquid-liquid extraction: The reaction solution was diluted with MEK, and then a water/methanol mixed solvent was added and processed to remove the aqueous phase from the reaction solution. The same operation was further performed once. ·Solvent replacement: The solvent was removed from the obtained reaction mixture using a rotary evaporator under reduced pressure and at 50°C. It was confirmed that the solid content concentration of the polymer solution was 27±2% by mass as measured by a heating drying moisture meter, and the operation of removing the solvent was discontinued. Thereafter, PGMEA was added so that the solid content concentration became 18% by mass, and the mixture was mixed until uniform. The same operation was repeated two more times: the solvent was removed under reduced pressure at 50°C, and the solid content concentration was adjusted to 27±2 mass% by measurement with a heating drying moisture meter. , further add PGMEA so that the solid content concentration becomes 18% by mass, and mix until uniform. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration became 30±3% by mass, and the mixture was stirred until it became uniform. Through the above operation, the solvent used in the reaction was removed and the solvent was replaced with PGMEA.

Through the above, the polymer P19 containing the structural units derived from maleic anhydride in the raw material polymer 3 was opened with A-TMM-3LM-N, 4-HBA and water, and the remaining (free) A- Resin mixture of TMM-3LM-N and residual (free) 4-HBA (polymer solution P19).

Under the same conditions as Preparation Example 3, the obtained polymer solution P19 was analyzed by gel permeation chromatography to measure the polymer P19, free polyfunctional (meth)acrylic acid compound and free monomer contained in the solution. The amount of functional (meth)acrylic compounds and the weight average molecular weight and polydispersity of polymer P19. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P19 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 20) A resin mixture (polymer solution P20) containing polymer P20 obtained by ring-opening the MA unit of raw material polymer 6 with a trifunctional (meth)acrylic acid compound and water was produced. The details are explained below. First, 99.93 g of MEK was added to 60.00 g of raw material polymer 6 (calculated from the input amount of raw material polymer 4 and converted to 0.230 mol in terms of MA) to prepare a solution. Next, 77.49 g of A-TMM-3LM-N was added to the solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 2 hours. Next, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70° C. for 2 hours. The obtained reaction solution was diluted with MEK, and treated with a formic acid aqueous solution and a citric acid aqueous solution, thereby removing the aqueous phase from the reaction solution. Furthermore, the same liquid-liquid extraction and solvent replacement as in Preparation Example 3 were performed. Thereby, a resin mixture (polymer solution P20) containing the polymer P20 obtained by ring-opening the MA unit of the raw material polymer 6 with a trifunctional (meth)acrylic acid compound and water was produced.

Under the same conditions as Preparation Example 3, the obtained polymer solution P20 was analyzed by gel permeation chromatography to measure the amounts of the polymer P20 and the free polyfunctional (meth)acrylic acid compound contained in the solution. Weight average molecular weight and polydispersity of polymer P20. The results are shown in Table 2. Furthermore, the amount of free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of polymer P20 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 21) The MA unit of the base polymer 9 was ring-opened with a monofunctional (meth)acrylic acid compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic acid compound (GMA). reaction to produce polymer P21. The details are explained below. First, 140.87 g of MEK was added to 60 g of the raw material polymer 9 (the mole calculated from the composition ratio calculated based on the GC measurement of the raw material polymer 9 and converted to MA was 0.242 mol) to prepare a solution. Next, 56.27 g (0.390 mol) of 4-HBA was added to the solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 6 hours. Thereafter, 26.62 g (0.187 mol) of GMA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours. The prepared reaction solution was diluted with MEK, and treated with a formic acid aqueous solution and a citric acid aqueous solution, thereby removing the water phase from the reaction solution. Thereafter, the polymer was purified by the reprecipitation method described below. ·Re-precipitation method: Use excess water to reprecipitate the polymer. The operation of washing the polymer powder obtained by reprecipitation with excess water was repeated twice. The reaction product obtained was dried at 40°C for 12 hours. Through the above, a polymer P21 in which the structural unit derived from maleic anhydride in the raw material polymer 9 was ring-opened with 4-HBA and reacted with GMA was obtained. GPC measurement was performed on the obtained polymer P21, and the weight average molecular weight and polydispersity of the polymer P21 were measured. The results are shown in Table 2. Furthermore, GPC measurement of polymer P21 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. From this, it was confirmed that the obtained polymer P21 contained neither an unreacted polyfunctional (meth)acrylic compound nor a monofunctional (meth)acrylic compound. Furthermore, through ¹³ C-NMR measurement, it was confirmed that the polymer P21 has a structure in which the structural unit derived from maleic anhydride of the raw material polymer 9 is ring-opened with 4-HBA and has a structure in which GMA is introduced.

(Preparation Example 22) A resin mixture (polymer solution P22) containing polymer P22 was prepared by ring-opening the MA unit of the raw material polymer 9 with a monofunctional (meth)acrylic acid compound (4-HBA), and then, It is obtained by reacting a (meth)acrylic acid compound (GMA) containing an epoxy group. The details are explained below. First, 140.87 g of MEK was added to 60 g of the raw material polymer 9 (the mole calculated from the composition ratio calculated based on the GC measurement of the raw material polymer 9 and converted to MA was 0.242 mol) to prepare a solution. Next, 56.27 g (0.390 mol) of 4-HBA was added to the solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 6 hours. Thereafter, 26.62 g (0.187 mol) of GMA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours. The obtained reaction solution was diluted with MEK, and treated with a formic acid aqueous solution and a citric acid aqueous solution, thereby removing the aqueous phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the following procedure, and then solvent replacement was performed. ·Liquid-liquid extraction: The reaction solution was diluted with MEK, and then a water/methanol mixed solvent was added and processed to remove the aqueous phase from the reaction solution. The same operation was further performed once. ·Solvent replacement: The solvent was removed from the obtained reaction mixture using a rotary evaporator under reduced pressure and at 50°C. It was confirmed that the solid content concentration of the polymer solution was 27±2% by mass as measured by a heating drying moisture meter, and the operation of removing the solvent was discontinued. Thereafter, PGMEA was added so that the solid content concentration became 18% by mass, and the mixture was mixed until uniform. The same operation was repeated two more times: the solvent was removed under reduced pressure at 50°C, and the solid content concentration was adjusted to 27±2 mass% by measurement with a heating drying moisture meter. , further add PGMEA so that the solid content concentration becomes 18% by mass, and mix until uniform. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration became 30±3% by mass, and the mixture was stirred until it became uniform. Through the above operation, the solvent used in the reaction was removed and the solvent was replaced with PGMEA.

Through the above, the polymer P22 containing the structural unit derived from maleic anhydride in the raw material polymer 9 was ring-opened with 4-HBA and reacted with GMA, and the remaining (free) 4-HBA and GMA were obtained. Resin mixture (polymer solution P22). The obtained polymer solution P22 was analyzed by gel permeation chromatography to measure the amount of polymer P22 contained in the solution, the amount of free monofunctional (meth)acrylic acid compounds (the total amount of 4-HBA and GMA), and the polymerization rate. The weight average molecular weight and polydispersity of substance P22. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P22 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express. In addition, the measurement conditions of gel permeation chromatography are as follows. ・As a GPC measurement device, TOSOH CORPORATION's HLC-8320GPC EcoSEC was used. The column temperature was set to 40.0°C, and the pump flow rate was set to 0.350 mL/min. ·Peak position (hold time) Polymer P22: Peak detected 20 minutes ago (peak with shorter retention time and larger molecular weight than 4-HBA, GMA, and A-TMM-3LM-N) A-TMM-3LM-N: 21.0～21.7 points 4-HBA, GMA: 21.7～23.0 points ·Measurement conditions: Analysis was performed using a differential refractive index detector (RI detector).

(Preparation Example 23) The MA unit of the raw material polymer 9 is ring-opened with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic acid compound (4-HBA), and then, the MA unit containing an epoxy group is ring-opened. The (meth)acrylic acid compound (GMA) is reacted to produce polymer P23. The details are explained below. First, 102.63 g of MEK was added to 60.00 g of the raw material polymer 9 (0.242 mole calculated from the composition ratio calculated based on the GC measurement of the raw material polymer 9 and converted to MA) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to the solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 2 hours. Thereafter, 33.76 g (0.234 mol) of 4-HBA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours. Thereafter, 19.97 g (0.140 mol) of GMA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours to prepare a reaction solution. The prepared reaction solution was diluted with MEK, and treated with a formic acid aqueous solution and a citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the following procedure, and then solvent replacement was performed. ·Liquid-liquid extraction: The reaction solution was diluted with MEK, and then a water/methanol mixed solvent was added and processed to remove the aqueous phase from the reaction solution. The same operation was further performed once. ·Solvent replacement: The solvent was removed from the obtained reaction mixture using a rotary evaporator under reduced pressure and at 50°C. It was confirmed that the solid content concentration of the polymer solution was 27±2% by mass as measured by a heating drying moisture meter, and the operation of removing the solvent was discontinued. Thereafter, PGMEA was added so that the solid content concentration became 18% by mass, and the mixture was mixed until uniform. The same operation was repeated two more times: the solvent was removed under reduced pressure at 50°C, and the solid content concentration was adjusted to 27±2 mass% by measurement with a heating drying moisture meter. , further add PGMEA so that the solid content concentration becomes 18% by mass, and mix until uniform. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration became 30±3% by mass, and the mixture was stirred until it became uniform. Through the above operation, the solvent used in the reaction was removed and the solvent was replaced with PGMEA. Thereafter, further purification was performed by the following reprecipitation method. • The polymer was reprecipitated with excess toluene. ·The operation of washing the polymer powder obtained by reprecipitation with excess toluene was repeated twice. ·The polymer powder washed twice with excess water was washed three times. ·The reaction product obtained was dried at 40°C for 12 hours.

Through the above, a polymer P23 was obtained in which the structural unit derived from maleic anhydride in the raw material polymer 9 was ring-opened with A-TMM-3LM-N and 4-HBA and reacted with GMA.

By GPC measurement of polymer P23, it was confirmed that the peaks of the polyfunctional (meth)acrylic compound, the monofunctional (meth)acrylic compound, and the epoxy group-containing (meth)acrylic compound used disappeared. Through this, it was confirmed that the obtained polymer P7 did not contain any unreacted (meth)acrylic acid compound, a (meth)acrylic acid compound not having a hydroxyl group, or an unreacted (meth)acrylic acid containing an epoxy group. compound.

The ¹ H-NMR spectrum of polymer P23 is shown in Figure 4 . In addition to the 5.8-6.7 ppm peak corresponding to 3H of the acryl group (-CH=CH ₂ ) shown in the ¹ H-NMR spectrum of polymer P23 in Figure 4, there is also a peak of 5.6-5.8 ppm represented by ×. And 6.0-6.1ppm, a peak corresponding to the methacrylyl group (-C(CH ₃ )=2H of CH ₂ (-C(CH ₃ )=CH ₂ of CH ₂ ) appeared. GPC measurement of polymer P7 , unreacted trifunctional (meth)acrylic acid compound (A-TMM-3LM-N), monofunctional (meth)acrylic acid compound (4-HBA), and (meth)acrylic acid containing epoxy groups were not observed. The peak of the compound (GMA) shows that the acryl group and the methacryl group derived from GMA were introduced into the polymer.

In addition, in the GPC measurement of the reaction solution before and after the ring-opening reaction and before and after the GMA addition reaction, before and after the ring-opening reaction, it was derived from the trifunctional (meth)acrylic acid compound (A-TMM-3LM-N), The peak of the (meth)acrylic acid compound (4-HBA) decreases, and the peak derived from GMA decreases before and after the GMA addition reaction. From this, it can also be seen that A-TMM-3LM-N, 4-HBA and GMA are introduced into the polymerization among things.

Furthermore, through ¹³ C-NMR measurement, it was confirmed that the polymer P23 has a structure in which the structural unit derived from maleic anhydride of the raw material polymer 9 was opened with A-TMM-3LM-N and 4-HBA and introduced with The structure of GMA.

(Preparation Example 24) A resin compound (polymer solution P24) containing polymer P24 was prepared by using the MA unit of the raw material polymer 9 with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monomer. It is obtained by ring opening a functional (meth)acrylic acid compound (4-HBA) and then reacting with a (meth)acrylic acid compound (GMA) containing an epoxy group. First, 102.63 g of MEK was added to 60.00 g of the raw material polymer 9 (0.242 mole calculated from the composition ratio calculated based on the GC measurement of the raw material polymer 9 and converted to MA) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to the solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 2 hours. Thereafter, 33.76 g (0.234 mol) of 4-HBA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours. Thereafter, 19.97 g (0.140 mol) of GMA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours to prepare a reaction solution. The prepared reaction solution was diluted with MEK, and treated with a formic acid aqueous solution and a citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the following procedure, and then solvent replacement was performed. ·Liquid-liquid extraction: The reaction solution was diluted with MEK, and then a water/methanol mixed solvent was added and processed to remove the aqueous phase from the reaction solution. The same operation was further performed once. ·Solvent replacement: The solvent was removed from the obtained reaction mixture using a rotary evaporator under reduced pressure and at 50°C. It was confirmed that the solid content concentration of the polymer solution was 27±2% by mass as measured by a heating drying moisture meter, and the operation of removing the solvent was discontinued. Thereafter, PGMEA was added so that the solid content concentration became 18% by mass, and the mixture was mixed until uniform. The same operation was repeated two more times: the solvent was removed under reduced pressure at 50°C, and the solid content concentration was adjusted to 27±2 mass% by measurement with a heating drying moisture meter. , further add PGMEA so that the solid content concentration becomes 18% by mass, and mix until uniform. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration became 30±3% by mass, and the mixture was stirred until it became uniform. Through the above operation, the solvent used in the reaction was removed and the solvent was replaced with PGMEA. Through the above, a resin mixture (polymer solution P24) containing polymer P24, residual (free) A-TMM-3LM-N, residual (free) 4-HBA, and residual (free) GMA was obtained. The polymer P24 By ring-opening the structural units derived from maleic anhydride in the raw material polymer 9 with A-TMM-3LM-N and 4-HBA, and then, with a (meth)acrylic acid compound (GMA) containing an epoxy group ) obtained by reaction. Under the same conditions as Preparation Example 23, the obtained polymer solution P24 was analyzed by gel permeation chromatography to measure the polymer P24, free polyfunctional (meth)acrylic acid compound and free monomer contained in the solution. The amount of functional (meth)acrylic compounds and the weight average molecular weight and polydispersity of polymer P24. The results are shown in Table 2.

(Preparation Example 25) The MA unit of the base polymer 7 was ring-opened with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N), water was added to further open the ring, and then, it was mixed with (methyl) containing an epoxy group. The acrylic acid compound (GMA) reacts to produce polymer P25. The details are explained below. First, 139.02 g of MEK was added to 60.00 g of the raw material polymer 7 (0.213 mol calculated from the composition ratio calculated based on the GC measurement of the raw material polymer 7 and converted to MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to the solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 2 hours to prepare a reaction solution. Next, without post-processing the obtained reaction solution, 1.50 g (0.083 mol) of water was added to the reaction solution, and the reaction was carried out at a temperature of 70° C. for 2 hours. Thereafter, 26.62 g (0.187 mol) of GMA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours to prepare a reaction solution. The prepared reaction solution was diluted with MEK, and treated with a formic acid aqueous solution and a citric acid aqueous solution, thereby removing the water phase from the reaction solution. Thereafter, the polymer was purified using the same liquid-liquid extraction, solvent replacement, and reprecipitation methods as in Preparation Example 23. Through the above, a polymer P25 was obtained in which the structural unit derived from maleic anhydride in the raw material polymer 7 was ring-opened with A-TMM-3LM-N and water and reacted with GMA. By GPC measurement of polymer P25, it was confirmed that the peak of the polyfunctional (meth)acrylic compound used and the (meth)acrylic compound containing an epoxy group disappeared. Through this, it was confirmed that the obtained polymer P25 did not contain an unreacted (meth)acrylic compound, a (meth)acrylic compound that did not have a hydroxyl group, or an unreacted epoxy group-containing (meth)acrylic compound. .

Furthermore, through ¹³ C-NMR measurement, it was confirmed that the polymer P25 has a structure in which the structural unit derived from maleic anhydride of the raw material polymer 7 is ring-opened with A-TMM-3LM-N and water, and has a structure in which GMA is introduced. structure.

(Preparation Example 26) A resin mixture (polymer solution P26) containing polymer P26 by ring-opening the MA unit of the raw material polymer 7 with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) was produced. , add water to further open the ring, and then react with a (meth)acrylic acid compound (GMA) containing an epoxy group to obtain it. The details are explained below. First, 139.02 g of MEK was added to 60.00 g of the raw material polymer 7 (0.213 mol calculated from the composition ratio calculated based on the GC measurement of the raw material polymer 7 and converted to MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to the solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 2 hours to prepare a reaction solution. Next, without post-processing the obtained reaction solution, 1.50 g (0.083 mol) of water was added to the reaction solution, and the reaction was carried out at a temperature of 70° C. for 2 hours. Thereafter, 26.62 g (0.187 mol) of GMA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours to prepare a reaction solution. The prepared reaction solution was diluted with MEK, and treated with a formic acid aqueous solution and a citric acid aqueous solution, thereby removing the water phase from the reaction solution. Thereafter, the polymer was purified using the same liquid-liquid extraction and solvent replacement methods as in Preparation Example 23, thereby obtaining a resin containing polymer P26, residual (free) A-TMM-3LM-N, and residual (free) GMA. Mixture (polymer solution P26). The polymer P26 is ring-opened by ring-opening the MA unit of the base polymer 7 with a trifunctional (meth)acrylic acid compound, adding water to further open the ring, and then, with an epoxy group-containing It is obtained by reacting with (meth)acrylic acid compound (GMA). The obtained polymer solution P26 was analyzed by gel permeation chromatography to measure the amount of the polymer P26 contained in the solution, the free polyfunctional (meth)acrylic acid compound, and the weight average molecular weight and polydispersity of the polymer P26. . The results are shown in Table 2. Furthermore, the amount of free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of polymer P26 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 27) It was produced in the same manner as Preparation Example 19 except that 60.00 g of the base polymer 10 was used (the mole calculated from the composition ratio calculated based on the GC measurement of the base polymer 10 and converted to MA was 0.128 mol). A resin mixture (polymer solution P27) containing polymer P27 obtained by ring-opening the MA unit of the raw material polymer 10 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound, and water. Under the same conditions as Preparation Example 19, the obtained polymer solution P27 was analyzed by gel permeation chromatography, and the polymer P27 and the free polyfunctional (meth)acrylic acid compound contained in the polymer solution P27 were measured. and the amount of free monofunctional (meth)acrylic compounds as well as the weight average molecular weight and polydispersity of polymer P27. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P27 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 28) It was produced in the same manner as Preparation Example 19 except that 60.00 g of the base polymer 11 was used (the mole calculated from the composition ratio calculated from the GC measurement of the base polymer 11 and converted to MA was 0.167 mol). A resin mixture (polymer solution P28) containing a polymer P28 obtained by ring-opening the MA unit of the raw material polymer 16 with a trifunctional (meth)acrylic acid compound, a monofunctional (meth)acrylic acid compound, and water. Under the same conditions as Preparation Example 19, the obtained polymer solution P28 was analyzed by gel permeation chromatography to measure the polymer P28 and the free polyfunctional (meth)acrylic acid compound contained in the polymer solution P28. and the amount of free monofunctional (meth)acrylic compounds as well as the weight average molecular weight and polydispersity of polymer P27. The results are shown in Table 2. Furthermore, the amount of free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of polymer P28 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(Preparation Example 29) A resin compound (polymer solution P29) containing polymer P29 was prepared by using the MA unit of the raw material polymer 11 with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monomer. It is obtained by ring opening a functional (meth)acrylic acid compound (4-HBA) and then reacting with a (meth)acrylic acid compound (GMA) containing an epoxy group. The details are explained below. First, 99.93 g of MEK was added to 60.00 g of the raw material polymer 11 (calculated from the composition ratio calculated based on the GC measurement of the raw material polymer 11 and converted to 0.167 mol in MA) to prepare a solution. Next, 77.49 g of A-TMM-3LM-N was added to the solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70° C. for 2 hours. Thereafter, 56.27 g (0.390 mol) of 4-HBA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours. Thereafter, 13.31 g (0.094 mol) of GMA was further added, and the reaction was carried out at a temperature of 70° C. for 4 hours to prepare a reaction solution. The obtained reaction solution was diluted with MEK, and treated with a formic acid aqueous solution and a citric acid aqueous solution, thereby removing the aqueous phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the following procedure, and then solvent replacement was performed. ·Liquid-liquid extraction: The reaction solution was diluted with MEK, and then water was added for treatment to remove the aqueous phase from the reaction solution. The same operation was further performed once. ·Solvent replacement: The solvent was removed from the obtained reaction mixture using a rotary evaporator under reduced pressure and at 50°C. It was confirmed that the solid content concentration of the polymer solution was 27±2% by mass as measured by a heating drying moisture meter, and the operation of removing the solvent was discontinued. Thereafter, PGMEA was added so that the solid content concentration became 18% by mass, and the mixture was mixed until uniform. The same operation was repeated two more times: the solvent was removed under reduced pressure at 50°C, and the solid content concentration was adjusted to 27±2 mass% by measurement with a heating drying moisture meter. , further add PGMEA so that the solid content concentration becomes 18% by mass, and mix until uniform. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration became 30±3% by mass, and the mixture was stirred until it became uniform. Through the above operation, the solvent used in the reaction was removed and the solvent was replaced with PGMEA.

Through the above, a resin mixture (polymer solution P29) containing polymer P29, residual (free) A-TMM-3LM-N, residual (free) 4-HBA, and residual (free) GMA was obtained. The polymer P29 By ring-opening the structural units derived from maleic anhydride in the raw material polymer 11 with A-TMM-3LM-N and 4-HBA, and then, with a (meth)acrylic acid compound (GMA) containing an epoxy group ) obtained by reaction. Under the same conditions as Preparation Example 24, the obtained polymer solution P29 was analyzed by gel permeation chromatography, and the polymer P29 and the free polyfunctional (meth)acrylic acid compound contained in the polymer solution P29 were measured. and the amount of free monofunctional (meth)acrylic compounds as well as the weight average molecular weight and polydispersity of polymer P29. The results are shown in Table 2. Furthermore, the amount of the free (meth)acrylic acid compound is based on the ratio (%) of the peak area of the free (meth)acrylic acid compound to the peak area of the polymer P29 in the gel permeation chromatography (GPC) spectrum of the resin mixture. )express.

(physical property evaluation) The acid value and double bond equivalent of each polymer P prepared in Preparation Examples 6, 8, 12, 14, 16, 18, 21 and 23 were measured using the method shown below.

(Acid value) The acid value of the polymer is measured by the following method. About 50 mg of polymer and about 5 mg of dimethyl terephthalate as internal standard material were measured and dissolved in DMSO-d6. ¹ H-NMR measurement was performed on this solution using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL Co., Ltd.). Based on the integrated value of the 4H peak (near 8.1 ppm) of the phenyl group of dimethyl terephthalate measured by ¹ H-NMR as the internal standard, the H peak (near 12.4 ppm) of the carboxyl group (-COOH) of the polymer ) to determine the amount of carboxyl groups. Then, the acid value (mgKOH/g) can be calculated from the amount. The larger the acid value, the greater the amount of carboxyl groups per unit mass of the polymer. The results are shown in Table 2. When the acid value is 50 gKOH/g or more, it can be considered that carboxyl groups necessary for the polymer to have sufficient developability are present in the polymer.

(Double bond equivalent) The double bond equivalent of the polymer was measured using the following method. ¹ H-NMR was measured in the same manner as the acid value measurement method described above. The amount of acryl group in the polymer was calculated from the integral ratio of the signal from the acryl group (5.6-5.8 ppm, 3H) in the obtained spectrum and the signal from the phenyl group (8.1 ppm, 4H) of the internal standard material ( mol/g), and calculated the methyl group in the polymer from the integral ratio of the signal from the methacrylyl group (5.6-5.8ppm, 2H) and the signal from the phenyl group of the internal standard material (8.1ppm, 4H) Acrylic acid group content (mol/g). Here, the signal originating from the methacryl group of 6.0-6.1 ppm is very small and overlaps with the signal of the acryl group, so it is calculated as the signal of the acryl group. The amount of double bonds (mol/g) was calculated from the sum of the calculated amount of acrylic groups (mol/g) and methacrylic groups (mol/g) in the polymer, and the double bond equivalent was calculated from the amount of double bonds. (g/mol). The results are shown in Table 2. The smaller the value of the double bond equivalent, the greater the amount of C=C double bonds per unit mass of the polymer.

[Table 2] Table 2 Preparation Example No. Polymer P No. (polymer solution No.) Raw polymer No. (Composition of raw polymer) Compounds that react with raw polymers Input ratio (mol ratio) (vs MA) Import ratio (mol ratio) (vs overall structure) Acid value (mgKOH/g) Double bond equivalent (g/mol) Weight average molecular weight Mw of polymer P Polydispersity Mw/Mn of polymer P Amount of residual polyfunctional (meth)acrylic compound (vs Polymer P) (based on GPC area) Amount of residual monofunctional (meth)acrylic compound (vs polymer P) (based on GPC area) Softening point (℃) (TMA) Melting point (℃) (Tg-DTA) Preparation Example 1 Polymer P1 Raw polymer 1 (NB/MAN/PEMP) 4-HBA (monofunctional) 1.250 - - - 4400 1.51 0.0% 0.0% 73 114 Preparation Example 2 Polymer P2 Raw polymer 1 (NB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.500 1.250 0.535 - - - 6900 1.56 0.0% 0.0% 119 144 Preparation Example 3 Polymer P3 (polymer solution P3) Raw polymer 1 (NB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.500 1.250 0.535 - - - 5500 1.49 46.7% 25.0% - - Preparation Example 4 Polymer P4 (polymer solution P4) Raw polymer 2 (NB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.500 1.250 0.535 - - - 4800 1.53 51.2% 28.6% - - Preparation Example 5 Polymer P5 (polymer solution P5) Raw polymer 2 (NB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.750 1.250 0.535 - - - 5100 1.54 73.7% 26.0% - - Preparation Example 6 Polymer P6 Raw polymer 4 (NB/FADB/MAN/PEMP) 4-HBA (monofunctional) 1.911 - 107 598 5800 1.60 0.0% 0.0% 96 114 Preparation Example 7 Polymer 7 (polymer solution P7) Raw polymer 3 (NB/FADB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.709 1.773 0.759 - - - 4100 1.40 47.3% 27.6% - - Preparation Example 8 Polymer P8 Raw polymer 4 (NB/FADB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.765 1.911 0.818 - 89 362 7400 1.99 0.0% 0.0% 70 120 Preparation Example 9 Polymer P9 (polymer solution P9) Raw polymer 4 (NB/FADB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.765 1.911 0.818 - - - 4600 1.47 49.9% 25.6% - - [table 3] Table 2 (continued) Preparation Example No. Polymer P No. (polymer solution No.) Raw polymer No. (Composition of raw polymer) Compounds that react with raw polymers Input ratio (mol ratio) (vs MA) Import ratio (mol ratio) (vs overall structure) Acid value (mgKOH/g) Double bond equivalent (g/mol) Weight average molecular weight Mw of polymer P Polydispersity Mw/Mn of polymer P Amount of residual polyfunctional (meth)acrylic compound (vs Polymer P) (based on GPC area) Amount of residual monofunctional (meth)acrylic compound (vs polymer P) (based on GPC area) Softening point (℃) (TMA) Melting point (℃) (Tg-DTA) Preparation Example 10 Polymer P10 (polymer solution P10) Raw polymer 4 (NB/FADB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 1.147 1.911 0.818 - - - 4600 1.44 79.3% 25.9% - - Preparation Example 11 Polymer P11 (polymer solution P11) Raw polymer 5 (NB/FADB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.653 1.632 0.698 - - - 5000 1.52 49.1% 25.4% - - Preparation Example 12 Polymer P12 Raw polymer 5 (NB/FADB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.653 1.632 0.698 - 104 316 8500 2.05 0.0% 0.0% 73 121 Preparation Example 13 Polymer P13 (polymer solution P13) Raw polymer 6 (NB/FADE/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.678 1.696 0.726 - - - 4400 1.47 48.8% 26.7% - - Preparation Example 14 Polymer P14 Raw polymer 6 (NB/FADE/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.678 1.696 0.726 - 101 310 7700 2.00 0.0% 0.0% 83 127 Preparation Example 15 Polymer P15 (polymer solution P15) Raw polymer 7 (NB/FABEH/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.733 1.831 0.784 - - - 4300 1.44 53.9% 27.0% - - Preparation Example 16 Polymer 16 Raw polymer 7 (NB/FABEH/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.733 1.831 0.784 - 100 303 7600 2.01 0.0% 0.0% 70 110 Preparation Example 17 Polymer P17 (polymer solution P17) Raw polymer 8 (NB/MADB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.635 1.587 0.679 - - - 4100 1.44 45.7% 24.3% - - Preparation Example 18 Polymer P18 Raw polymer 8 (NB/MADB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.635 1.587 0.679 - 103 302 6900 2.05 0.0% 0.0% 78 109 Preparation Example 19 Polymer P19 (polymer solution P19) Raw polymer 3 (NB/FADB/MAN/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.709 1.773 0.759 - - - 3800 1.38 5.1% 0.3% - - Preparation Example 20 Polymer P20 (polymer solution P20) Raw polymer 6 (NB/FADE/MAN/PEMP) A-TMM-3LM-N (3 functional) water 0.678 0.726 - - - 5500 1.42 52.1% 0.0% - - [Table 4] Table 2 (continued) Preparation Example No. Polymer P No. (polymer solution No.) Raw polymer No. (Composition of raw polymer) Compounds that react with raw polymers Input ratio (mol ratio) (vs MA) Import ratio (mol ratio) (vs overall structure) Acid value (mgKOH/g) Double bond equivalent (g/mol) Weight average molecular weight Mw of polymer P Polydispersity Mw/Mn of polymer P Amount of residual polyfunctional (meth)acrylic compound (vs Polymer P) (based on GPC area) Amount of residual monofunctional (meth)acrylic compound (vs polymer P) (based on GPC area) Softening point (℃) (TMA) Melting point (℃) (Tg-DTA) Preparation Example 21 Polymer P21 Raw polymer 9 (NB/MAN/FADB/PEMP) 4-HBA (monofunctional) GMA 1.608 0.772 0.210 0.019 74 552 4,600 1.54 0.0% 0.0% 53 73 Preparation Example 22 Polymer P22 (polymer solution P22) Raw polymer 9 (NB/MAN/FADB/PEMP) 4-HBA (monofunctional) GMA 1.608 0.772 - - - 4,600 1.41 0.0% 0.8% - - Preparation Example 23 Polymer P23 Raw polymer 9 (NB/MAN/FADB/PEMP) A-TMM-3LM-N (3 functional) 4-HBA (mono functional) GMA 0.322 0.965 0.579 0.046 0.133 0.016 74 431 9,100 2.69 0.0% 0.0% 104 128 Preparation Example 24 Polymer P24 (polymer solution P24) Raw polymer 9 (NB/MAN/FADB/PEMP) A-TMM-3LM-N (3 functional) 4-HBA (mono functional) GMA 0.322 0.965 0.579 - - - 5,300 1.52 5.1% 0.8% - - Preparation Example 25 Polymer P25 Raw polymer 7 (NB/MAN/FABEH/PEMP) A-TMM-3LM-N (3 functional) Water GMA 0.653 1.632 0.698 - - - 8,900 2.51 0.0% 0.0% 88 107 Preparation Example 26 Polymer P26 (polymer solution P26) Raw polymer 7 (NB/MAN/FABEH/PEMP) A-TMM-3LM-N (3 functional) Water GMA 0.653 1.632 0.698 - - - 4,700 1.44 12.5% 0.1% - - Preparation Example 27 Polymer P27 (polymer solution P27) Raw polymer 10 (NB/MAN/FADB/PhMI/PEMP) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 1.390 3.477 1.502 - - - 3,200 1.27 94.7% 51.6% - - Preparation Example 28 Polymer P28 (polymer solution P28) Raw polymer 11 (NB/MAN/FADB) A-TMM-3LM-N (trifunctional) 4-HBA (monofunctional) water 0.934 2.335 1.000 - - - 4,400 1.32 64.4% 30.9% - - Preparation Example 29 Polymer P29 (polymer solution P29) Raw polymer 11 (NB/MAN/FADB) A-TMM-3LM-N (3 functional) 4-HBA (mono functional) GMA 0.701 2.335 0.560 - - - 5,000 1.50 66.6% 35.2% - -

[Examples 1 to 24, Comparative Examples 1 to 5] In each of the Examples and Comparative Examples, a resin composition was prepared and evaluated for the following items. ＜Evaluation＞ [Alkali dissolution rate of resin composition] The polymers P1, P2, P6, P8, P12, P14, P16, P18, P21, P23, P25 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to produce resin compositions 1, 2, 6, 8, 12, 14, 16, 18, 21, 23, and 25 having a solid content concentration of 30% by mass. Next, the above-mentioned resin compositions 1, 2, 6, 8, 12, 14, 16, 18, 12, 14, 16, 18, 21, 23, 25 are spin-coated on the wafer or prepared according to Preparation Examples 3 to 5 and 7. , 9, 10, 11, 13, 15, 17, 19, 20, 22, 24, 26~29, polymer solutions P3~P5, P7, P9, P10, P11, P13, P15, P17, P19 , resin compositions 3 to 5, 7, 9, 10, 11, 13, 15, 17, 19, 20, 22, 24, 26 to 29 composed of P20, P22, P24, P26 to P29, and dry the PGMEA, Then, it was prebaked at a temperature of 100° C. for 2 minutes to produce a resin film with a film thickness of approximately 2 μm. The resin film and the wafer were immersed in a 2% sodium carbonate aqueous solution at a temperature of 23°C, and the dissolution rate of the resin film was measured. The dissolution rate is calculated by visually observing the immersed wafer, measuring the time until the resin film dissolves and no interference pattern is visible, and dividing the film thickness by the time. The results are shown in Table 3. If the alkali dissolution rate is 20 nm/s or more, it can be used as a photosensitive material without any problem. If it is 100 nm/s or more, the developability can be considered to be good. If it is 500 nm/s or more, it can be considered to be even better. , and further, if it is 1000 nm/s or more, it can be considered to be particularly good.

[Softening point of raw polymer] The softening points of raw material polymers 1 to 11 were measured by the following method. First, 0.1 to 1.0 mg of the polymer to be measured (raw material polymers 1 to 11) was placed in an aluminum sample pan, and a differential thermal analysis device (manufactured by Hitachi High-Tech Science Corporation, "EXSTAR TMA/ SS6100") measured the softening point. The measurement mode was compression, the load was set to 30 mN, and the temperature was raised at a heating rate of 3°C/min in the range of 30°C to 200°C. If the sample softens due to temperature rise, the sample deforms, which is detected as the displacement amount (μm), the extension of the straight line portion without displacement on the low temperature side or the tangent line of the minimum portion of the displacement speed and the maximum displacement speed. The intersection point of the tangent lines of the parts is set as the softening point. As an example, the TMA spectrum of raw material polymer 4 is shown in FIG. 3 . The measurement results of the softening point are shown in Table 1. If the softening point of the raw material polymer is 130°C or lower, it can be said to be low. If it is 120°C or lower, it can be said to be lower. If it is 100°C or lower, it can be said to be particularly lower. If it is 90°C or lower, it can be said to be particularly lower. It can be said that it is even lower.

[Melting point of raw material polymer] The melting points of raw material polymers 1 to 11 were measured by the following method. First, 1 to 2 mg of the polymer to be measured (raw material polymers 1 to 11) are placed in an aluminum sample pan, and a differential thermal analysis device (manufactured by Hitachi High-Tech Science Corporation, "STA7200RV") is used in a nitrogen environment. While observing the image, the temperature was raised from 30°C at a temperature increase rate of 10°C/min. The temperature at which the sample begins to melt is visually confirmed and used as the melting point. If the melting point of the raw material polymer is 160°C or lower, it can be said to be low. If it is 140°C or lower, it can be said to be lower. If it is 120°C or lower, it can be said to be particularly lower. If it is 110°C or lower, it can be said to be particularly low. Further especially lower. The results are shown in Table 1.

[Softening point of polymer P] The polymers P1, P2, P6, P8, P12, P14, P16, and P18 obtained in Preparation Examples 1, 2, 6, 8, 12, 14, 16, 18, 21, 23, and 25 were measured using the following method. , P21, P23, P25 softening point. First, place 0.1-1.0 mg of the polymer to be measured (polymer P1, P2, P6, P8, P12, P14, P16, P18, P21, P23, P25) into an aluminum sample pan and use it in a nitrogen environment The softening point was measured using a differential thermal analysis device ("EXSTAR TMA/SS6100" manufactured by Hitachi High-Tech Science Corporation). The measurement mode was compression, the load was set to 30 mN, and the temperature was raised at a heating rate of 3°C/min in the range of 30°C to 200°C. If the sample softens due to temperature rise, the sample deforms, which is detected as the displacement amount (μm), the extension of the straight line portion without displacement on the low temperature side or the tangent line of the minimum portion of the displacement speed and the maximum displacement speed. The intersection point of the tangent lines of the parts is set as the softening point. The results are shown in Table 2. If the softening point of the polymer P is 110°C or lower, it can be said to be low. If it is 90°C or lower, it can be said to be lower. If it is 80°C or lower, it can be said to be particularly lower. If it is 70°C or lower, it can be said to be particularly lower. It can be said that it is even lower.

[Melting point of polymer P] The polymers P1, P2, P6, P8, P12, P14, P16, and P18 obtained in Preparation Examples 1, 2, 6, 8, 12, 14, 16, 18, 21, 23, and 25 were measured using the following method. , P21, P23, P25 melting point. First, put 1 to 2 mg of the polymer to be measured (polymers P1, P2, P6, P8, P12, P14, P16, P18, P21, P23, P25) into an aluminum sample pan, and use differential pressure in a nitrogen environment. The thermal analysis device (manufactured by Hitachi High-Technologies Corporation, "STA7200RV") was heated from 30°C at a temperature increase rate of 10°C/min while observing the image. The temperature at which the sample begins to melt is visually confirmed and used as the melting point. The results are shown in Table 2. If the melting point of the polymer P is 140°C or lower, it can be said to be low. If it is 130°C or lower, it can be said to be lower. If it is 120°C or lower, it can be said to be particularly lower. If it is 110°C or lower, it can be said to be lower. Said further, it is even lower.

[Softening Point of Cured Material of Photosensitive Resin Composition] The polymer P1 obtained in Preparation Examples 1, 2, 6, 8, 12, 14, 16, 18, 21, 23, and 25 was measured by the following method. , P2, P6, P8, P12, P14, P16, P18, P21, P23, P25 or Preparation Examples 3 to 5, 7, 9, 10, 11, 13, 15, 17, 19, 20, 22, 24, 26 Softening points of photosensitive resin compositions produced from polymer solutions P3 to P5, P7, P9, P10, P11, P13, P15, P17, P19, P20, P22, P24, P26 to P29 obtained in step 29. First, the following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid content concentration became 30 mass %, and a photosensitive resin composition was obtained. ·Polymers P1, P2, P6, P8, P12, P14, P16, P18, P21, P23, P25 (preparation examples 1, 2, 6, 8, 12, 14, 16, 18, 21, 23, 25, respectively) Polymer P) or resin mixtures 3 to 5, 7, 9, 10, 11, 13, 15, 17, 19, 20, 22, 24, 26 to 29 (preparation examples 3 to 5, 7 respectively) obtained in , 9, 10, 11, 13, 15, 17, 19, 20, 22, 24, 26~29 polymer solutions P3~P5, P7, P9, P10, P11, P13, P15, P17, P19, P20, P22, P24, P26～P29): 100 parts by mass (here, for resin mixtures 3～5, 7, 9, 10, 11, 13, 15, 17, 19, 20, 22, 24, 26～29, The total amount of the solid content (polymers P3 to P5, P7, P9, P10, P11, P13, P15, P17, P19, P20, P22, P24, P26 to P29) and the polyfunctional (meth)acrylic compound) is Weighed in 100 parts by mass. ) · Photopolymerization initiator (Irgacure OXE01 manufactured by BASF): 5 parts by mass. The obtained photosensitive resin composition was poured into the Teflon adhesive tape (NITOFLON adhesive tape, No. 903UL) without any gaps. Thickness 0.08mm, width 25mm, length 10mm), Nitto Denko Corporation) in a container with dimensions 2cm × 2cm, height 5mm, and then vacuum dried at 40°C for 16 hours to remove the solvent. Thereafter, the film was exposed to g+h+i rays using a g+h+i ray mask aligner (PLA-600F) manufactured by Canon Inc. at an exposure dose of 100 mJ/cm ² . After exposure, the hardened material was peeled off from the Teflon adhesive tape, and a hardened material of the photosensitive resin composition was obtained. 0.1 to 1.0 mg of the cured product of the photosensitive resin composition to be measured was placed in an aluminum sample pan, and measured using a differential thermal analysis device ("EXSTAR TMA/SS6100" manufactured by Hitachi High-Tech Science Corporation) in a nitrogen environment. softening point. The measurement mode was compression, the load was set to 30 mN, and the temperature was raised in the range of 30°C to 200°C at a heating rate of 1°C/min. If the sample softens due to temperature rise, the sample deforms, which is detected as the displacement amount (μm), the extension of the straight line portion without displacement on the low temperature side or the tangent line of the minimum portion of the displacement speed and the maximum displacement speed. The intersection point of the tangent lines of the parts is set as the softening point. Table 3 shows the evaluation results of the softening point of the cured product of the photosensitive resin composition evaluated based on the following standards. A: The softening point is lower than 100°C. B: The softening point is 100°C or higher. If the softening point of the cured product of the photosensitive resin composition is lower than 100°C, it can be said that the softening point is low and the pattern formability is good.

[Sensitivity evaluation of photosensitive resin composition 1 (exposure amount at which film residual rate becomes 90% or more)] First, the following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid content concentration became 30 mass %, and a photosensitive resin composition was obtained. ·Polymers P1, P2, P6, P8, P12, P14, P16, and P18 (polymer P of Preparation Examples 1, 2, 6, 8, 12, 14, 16, and 18, respectively) or resin compositions 3 to 5 , 7, 9, 10, 11, 13, 15, 17, 19, 20 (respectively the polymer solutions P3~ of Preparation Examples 3~5, 7, 9, 10, 11, 13, 15, 17, 19, and 20 P5, P7, P9, P10, P11, P13, P15, P17, P19, P20): 100 parts by mass (Here, for resin compositions 3 to 5, 7, 9, 10, 11, 13, 15, 17, 19, and 20, the solid content (polymers P3 to P5, P7, P9, P10, P11, P13 , P15, P17, P19, P20) and the total amount of the polyfunctional (meth)acrylic compound) were weighed so that it became 100 parts by mass. ) ·Polyfunctional acrylate (dineopenterythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by mass ·Photopolymerization initiator (Irgacure OXE01 manufactured by BASF): 5 parts by mass · Adhesion additive (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by mass ·Surface active agent (manufactured by DIC Corporation, F-556): 0.5 parts by mass

The obtained photosensitive resin composition was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds to obtain a thickness of about 3.0 μm (±0.3 μm) film A. The film A is separated from a mask having a gradation of 1 to 100% light shielding rate, and a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. is used to 100 mJ/cm ² The exposure amount was g+h+i ray exposure. After exposure, the film was developed in a 2.0 mass% sodium carbonate aqueous solution at 23°C for 60 seconds (immersed together with the wafer), thereby obtaining a film exposed and developed at each exposure dose of 1 to 100 mJ/cm ² B. Based on the film thicknesses of film A and film B obtained by the above method, the remaining film rate is calculated from the following formula. Remaining film rate (%) = (film thickness of film B at each exposure dose/film thickness of film A) × 100 Then, the exposure dose at which the film remaining rate became 90% or more was defined as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. If the exposure dose at which the residual film rate becomes 90% or more is 25 mJ/cm ² or less, it can be used as a photosensitive composition without any problem. If it is 20 mJ/cm ² or less, the sensitivity can be considered to be good. If it is 15 mJ/cm 2 If it is 12 mJ/cm ² or less, it can be considered to be better, and if it is 12 mJ/cm ² or less, it can be considered to be particularly good.

[Sensitivity Evaluation 2 of the Photosensitive Resin Composition (Residual Film Rate after Exposure at Low Exposure)] (Remaining Film Rate at an Exposure of 5 mJ/cm ² ) The photosensitive resin prepared in the above sensitivity evaluation 1 The composition was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds to obtain a 3.0 μm thick (±0.3 μm) film A. The film A was separated from a grayscale mask with a light shielding rate of 1 to 100%, and the g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. was used to expose the film A at an exposure dose of 5 mJ/cm ² Exposure to g+h+i rays was performed. After exposure, the film was developed in a 2.0 mass% sodium carbonate aqueous solution at 23°C for 60 seconds (immersed together with the wafer), thereby obtaining film B. Based on the film thicknesses of film A and film B obtained by the above method, the remaining film rate is calculated from the following formula. Residual film rate (%) = (film thickness of film B at each exposure dose/film thickness of film A) × 100. The results are shown in Table 3. The greater the residual film rate at the exposure dose of 5 mJ/cm ² , the better Hardening with low exposure can be considered to have good sensitivity.

(Remaining film rate at an exposure dose of 10mJ/ ^cm2 ) The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and inlaid at 100 ℃ and baked on a hot plate for 120 seconds to obtain film A with a thickness of 3.0 μm (±0.3 μm). The film A is separated from a gray mask having a light shielding rate of 1 to 100%, and a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. is used to expose the film A at an exposure dose of 10 mJ/cm ² Exposure to g+h+i rays was performed. After exposure, the film was developed in a 2.0 mass% sodium carbonate aqueous solution at 23°C for 60 seconds (immersed together with the wafer), thereby obtaining film B. Based on the film thicknesses of film A and film B obtained by the above method, the remaining film rate is calculated from the following formula. Residual film rate (%) = (film thickness of film B at each exposure dose/film thickness of film A) × 100. The results are shown in Table 3. The greater the residual film rate at the exposure dose of 10mJ/ ^cm2 , the better Hardening with low exposure can be considered to have good sensitivity.

[Alkali dissolution rate of photosensitive resin composition (2.0 mass% sodium carbonate aqueous solution)] The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on the wafer, and the PGMEA was dried, and then prebaked at a temperature of 100° C. for 2 minutes to produce a resin film with a film thickness of approximately 2 μm. The resin film and the wafer were immersed in a 2% sodium carbonate aqueous solution at a temperature of 23°C, and the dissolution rate of the resin film was measured. The dissolution rate is calculated by visually observing the immersed wafer, measuring the time until the resin film dissolves and no interference pattern is visible, and dividing the film thickness by the time. The results are shown in Table 3. If the alkali dissolution rate is 100 nm/s or more, it can be used as a photosensitive material without any problem. If it is 200 nm/s or more, the developability can be considered to be good. If it is 400 nm/s or more, it can be considered to be even better. , and further, if it is 700 nm/s or more, it can be considered to be particularly good.

[Yellow Index] The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on EAGLE XG glass (manufactured by Corning Incorporated Co., Ltd., thickness 0.5 mm), and baked on a hot plate at 100°C. Bake for 120 seconds to obtain a film with a thickness of approximately 3.0 μm (±0.1 μm). Next, the film was exposed to g+h+i rays using a g+h+i ray mask aligner (PLA-600F) manufactured by Canon Inc. at an exposure dose of 100 mJ/cm ² . After exposure, the film was developed in a 2.0 mass% sodium carbonate aqueous solution at 23°C for 60 seconds (immersed together with the wafer), thereby obtaining a film exposed and developed at an exposure dose of 100 mJ/cm ² . The film was heat treated at 230°C under air for 30 minutes. After the film was cooled in air at room temperature, the film was again heat-treated at 230° C. in air for 30 minutes. The same operation was repeated, and heat treatment under air for 30 minutes was performed a total of three times. Using a colorimeter CR-5 (manufactured by Konica Minolta, Inc.), the yellowness index (YI) of the film obtained by the above method was measured three times while changing the measurement location, and the average value was used as the value of YI. The measurement type is transmission measurement, and 100% correction uses uncoated EAGLE XG glass (manufactured by Corning Incorporated Co., Ltd., thickness 0.5mm). The results are shown in Table 3. If the yellow index is 1.30 or less, it can be used as a photosensitive material without any problem. If it is 1.10 or less, the heat discoloration resistance can be considered to be good. If it is 1.00 or less, the heat discoloration resistance can be considered to be better. Furthermore, If it is 0.85 or less, it can be regarded as particularly good.

Table 3 shows the results of developability evaluation and sensitivity evaluation.

[table 5] table 3 Example No. Resin composition No. Polymer No. (Polymer solution No.) Performance evaluation of resin compositions Performance evaluation of cured products of photosensitive resin compositions Performance evaluation of photosensitive resin compositions Alkali dissolution rate DR (nm/s) Evaluation of softening point Yellow index (YI) after heat treatment Alkali dissolution rate DR (nm/s) 90% residual film exposure (mJ/cm ² ) Residual film rate when exposed to 5mJ/ ^cm2 Residual film rate when exposed to 10mJ/ ^cm2 Comparative example 1 Resin composition 1 Polymer P1 172 A 0.99 479 50 twenty three% 38% Comparative example 2 Resin composition 2 Polymer P2 149 B 1.12 301 20 0% 40% Comparative example 3 Resin composition 3 Polymer P3 (polymer solution P3) >1000 B 0.88 1174 30 55% 80% Comparative example 4 Resin composition 4 Polymer P4 (polymer solution P4) >1000 B 0.88 1460 15 60% 86% Comparative example 5 Resin composition 5 Polymer P5 (polymer solution P5) >1000 B 0.77 2217 50 29% 85% Example 1 Resin composition 6 Polymer P6 116 A 1.05 460 25 2% 78% Example 2 Resin composition 7 Polymer P7 (polymer solution P7) >1000 A 0.85 834 18 69% 79% Example 3 Resin composition 8 Polymer P8 67 A 1.01 296 15 44% 84% Example 4 Resin composition 9 Polymer P9 (polymer solution P9) >1000 A 0.74 178 12 69% 86% Example 5 Resin composition 10 Polymer P10 (polymer solution P10) >1000 A 0.70 447 20 61% 84% Example 6 Resin composition 11 Polymer P11 (polymer solution P11) >1000 A 0.75 443 12 62% 87% Example 7 Resin composition 12 Polymer P12 157 A 0.95 273 12 54% 87% Example 8 Resin composition 13 Polymer P13 (polymer solution P13) >1000 A 0.74 288 15 62% 83% Example 9 Resin composition 14 Polymer P14 107 A 0.95 370 13 58% 85% Example 10 Resin composition 15 Polymer P15 (polymer solution P15) >1000 A 0.77 215 15 66% 79% [Table 6] Table 3 (continued) Example No. Resin composition No. Polymer No. (Polymer solution No.) Performance evaluation of resin compositions Performance evaluation of cured products of photosensitive resin compositions Performance evaluation of photosensitive resin compositions Alkali dissolution rate DR (nm/s) Evaluation of softening point Yellow index (YI) after heat treatment Alkali dissolution rate DR (nm/s) 90% residual film exposure (mJ/cm ² ) Residual film rate when exposed to 5mJ/ ^cm2 Residual film rate when exposed to 10mJ/ ^cm2 Example 11 Resin composition 16 Polymer P16 52 A 0.99 151 13 45% 77% Example 12 Resin composition 17 Polymer P17 (polymer solution P17) >1000 A 0.75 561 15 64% 83% Example 13 Resin composition 18 Polymer P18 157 A 0.98 385 15 3% 79% Example 14 Resin composition 19 Polymer P19 (polymer solution P19) 89 A 0.88 355 18 61% 76% Example 15 Resin composition 20 Polymer P20 (polymer solution P20) >1000 A 0.81 181 15 63% 77% Example 16 Resin composition 21 Polymer P21 31 A 0.97 158 40 8% 71% Example 17 Resin composition 22 Polymer P22 (polymer solution P22) 45 A 0.99 131 45 2% 67% Example 18 Resin composition 23 Polymer P23 28 A 1.09 124 5 4% 92% Example 19 Resin composition 24 Polymer P24 (polymer solution P24) 47 A 1.01 151 6 63% 88% Example 20 Resin composition 25 Polymer P25 65 A 1.10 210 7 4% 89% Example 21 Resin composition 26 Polymer P26 (polymer solution P26) 67 A 1.02 232 8 56% 75% Example 22 Resin composition 27 Polymer P27 (polymer solution P27) 64 A 1.04 271 20 65% 70% Example 23 Resin composition 28 Polymer P28 (polymer solution P28) 30 A 1.24 145 20 34% 71% Example 24 Resin composition 29 Polymer P29 (polymer solution P29) 28 A 1.29 124 18 36% 70%

According to the comparison between raw material polymers 3 to 11 and raw material polymers 1 and 2, compared with raw material polymers 1 and 2, raw material polymers 3 to 11 containing structural units derived from unsaturated dicarboxylic acid dialkyl ester, Its softening point or melting point drops significantly. In addition, polymers P6, P8, P12, P14, P16, P18, P21, P23, and P25 containing structural units derived from unsaturated dialkyl dicarboxylate have a softening point of 110°C or less and a melting point of 140°C. Below, it has a low softening point and low melting point. The softening point of the cured product of the photosensitive resin composition produced from the polymer of Comparative Examples 2 to 5 that does not contain a structural unit derived from unsaturated dialkyl dicarboxylate is 100° C. or higher. On the other hand, the softening point of the cured product of the photosensitive resin composition made from the polymer of Examples 1 to 24 containing a structural unit derived from unsaturated dialkyl dicarboxylate did not reach 100°C. It is easily melted by heat and is expected to have good processability and patterning properties in photolithography processing. Furthermore, the photosensitive resin composition containing the polymers of Examples 1 to 24 has alkali solubility, sensitivity, and heat discoloration resistance in a well-balanced manner. The cured product of the photosensitive resin composition made from the polymer of Comparative Example 1 has a softening point lower than 100°C, but the sensitivity of the photosensitive resin composition is insufficient. Photosensitive resin compositions of Examples 2 to 15 and 18 to 24 containing a structural unit derived from an unsaturated dialkyl dicarboxylate and a polymer having a structure ring-opened with a polyfunctional (meth)acrylic compound , the residual film rate becomes more than 90%, the exposure is lower, and the sensitivity is particularly excellent. Also, a polymer containing a structural unit derived from an unsaturated dialkyl dicarboxylate and having a structure ring-opened with a polyfunctional (meth)acrylic compound, and containing a carbon number 1 derived from a thiol group-containing compound. The photosensitive resin compositions of Examples 1 to 22, which are polymers of 1 to 6 valent organic groups of ~30, have a low yellow index and are more excellent in heat discoloration resistance.

＜Preparation of color filter/gap＞ A colored photosensitive resin composition was prepared by further adding an appropriate amount of pigment dispersion NX-061 (Dainichiseika Color & Chemicals Mfg.) to the photosensitive resin composition prepared in Examples 1 to 24. Co., Ltd. (manufactured, green). A green color filter can be formed by forming a film on a substrate and subjecting it to exposure, alkali development, etc. In addition, as the pigment dispersion liquid, a blue or red color filter can be formed by using NX-053 (blue), NX-032 (red), etc. manufactured by this company instead of NX-061.

＜Preparation of black matrix/black bank/black gap＞ A black photosensitive resin composition was prepared by further adding an appropriate amount of carbon black dispersion NX-595 (Dainichiseika Color & Chemicals Mfg.) to the photosensitive resin composition prepared in Examples 1 to 24. Co., Ltd.). The film is formed on a substrate and subjected to exposure, alkali development, etc., thereby forming a black matrix/black bank/black spacer.

This application claims priority based on Japanese Patent Application Application No. 2022-008091 filed on January 21, 2022, and the entire disclosure of the application is incorporated herein by reference.

10:Substrate 11: black matrix 12: Color filter 13:Protective film 14:Transparent electrode layer

[Fig. 1] is a diagram (cross-sectional view) schematically showing an example of the structure of a liquid crystal display device and/or a solid-state imaging element. [Fig. 2] It is the ¹³ C-NMR spectrum of raw material polymer 4. [Fig. 3] shows the TMA spectrum of the raw material polymer 4. [Fig. 4] is a ¹ H-NMR spectrum of polymer P23 obtained in Preparation Example 23.

10:Substrate

11: black matrix

12: Color filter

13:Protective film

14:Transparent electrode layer

Claims (25)

A polymer containing: a structural unit represented by formula (NB); a structural unit represented by formula (AD); and a structural unit selected from formula (1-2) and formula (1-3) At least 1 structural unit among the structural units, wherein, In the general formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2, In the formula (AD), R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. , In formula (1-2), R ^p is a group having two or more (meth)acrylyl groups, R ²² is a hydrogen atom or an organic group having 1 to 3 carbon atoms, In formula (1-3), R ^s is a group having one (meth)acrylyl group, and R ²² is a hydrogen atom or an organic group having 1 to 3 carbon atoms. The polymer of claim 1 further contains a structural unit represented by formula (1-1), In the formula (1-1), R ²¹ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, Z is a group containing one or more (meth)acrylyl groups, Q is a hydrogen atom or a substituted or unsubstituted group. Substituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. When Q is the aforementioned alkyl group and X is the aforementioned alkylene group, Q and X may condense to form a cyclic group. Such as the polymer of claim 1, which further contains structural units represented by formula (1-4), In formula (1-4), R ²² is a hydrogen atom or an organic group having 1 to 3 carbon atoms. The polymer of claim 1, which further contains at least one selected from the structural unit represented by formula (1) and the structural unit represented by formula (2), In formula (1), R ^p is a group having two or more (meth)acrylyl groups, R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, In formula (2), R ^s is a group having one (meth)acrylyl group, and R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. The polymer of claim 1 further contains a structural unit represented by formula (3), In formula (3), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. The polymer of claim 2, which further contains at least one selected from the structural unit represented by formula (8) and the structural unit represented by formula (9), In formula (8), Z is a group containing one or more (meth)acrylyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and X represents an oxygen atom or A substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. When Q is the aforementioned alkyl group and X is the aforementioned alkylene group, Q ^and (meth)acrylyl group, R ²¹ and R ²² are hydrogen atoms or organic groups with 1 to 3 carbon atoms, In formula (9), Z is a group containing one or more (meth)acrylyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and X represents an oxygen atom or an alkyl group having 1 to 6 carbon atoms. A substituted or unsubstituted alkylene group with 1 to 4 carbon atoms. When Q is the aforementioned alkyl group and X is the aforementioned alkylene group, Q ^and group) acrylic group, R ²¹ and R ²² are hydrogen atoms or organic groups having 1 to 3 carbon atoms. Such as the polymer of claim 2, which further contains structural units represented by formula (5), In formula (5), Z is a group containing one or more (meth)acrylyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and X represents an oxygen atom or Substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. When Q is the aforementioned alkyl group and X is the aforementioned alkylene group, Q and X may be condensed to form a cyclic group. R ²¹ and R ²² are hydrogen atoms. Or an organic group having 1 to 3 carbon atoms. The polymer of claim 2 further contains a structural unit represented by formula (6), In formula (6), Z is a group containing one or more (meth)acrylyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and X represents an oxygen atom or Substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. When Q is the aforementioned alkyl group and X is the aforementioned alkylene group, Q and X may be condensed to form a cyclic group. R ²¹ and R ²² are hydrogen atoms. Or an organic group having 1 to 3 carbon atoms. The polymer of claim 1 further contains a structural unit represented by formula (MA), In the formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. The polymer of claim 1, wherein the polymer contains the structural unit represented by the aforementioned formula (1-2), and R ^p in the aforementioned formula (1-2) is selected from the group represented by the formula (1b), At least one of the base represented by formula (1c) and the base represented by formula (1d), In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and the plurality of R may be the same or different. X ¹ is a single bond, an alkylene group with 1 to 6 carbon atoms, or -ZX-. The base ^, where Z is -O- ^or -OCO-, Alkylene group or a group represented by -X'-Z'-, where X' is an alkylene group with 1 to 6 carbon atoms, Z' is -O- or -COO-, and X ² is an alkylene group with 1 to 12 carbon atoms The organic radical with (k+1) valence, In formula (1c), k ^, R, X ¹ and X ² are respectively synonymous with R, k, ^{X 1 and} They may be the same or different from each other. X ³ is a single bond or a divalent organic group having 1 to 6 carbon atoms. X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms. ⁶ is a divalent organic group having 1 to 6 carbon atoms, In formula (1d), n is an integer of 2 to 5, and R is independently a hydrogen atom or a methyl group. The polymer of claim 1, wherein the polymer contains the structural unit represented by the aforementioned formula (1-3), R ^s in the aforementioned formula (1-3) is a group represented by the formula (2a), In formula (2a), X ¹⁰ is a divalent organic group, and R is a hydrogen atom or a methyl group. The polymer of claim 1 further contains a structural unit represented by formula (MI), In the formula (MI), R ³¹ is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R ³² and R ³³ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. The polymer of claim 1, wherein the polymer has a structure represented by formula (P3), In formula (P3), n is an integer from 1 to 6, p, q and r represent the molar content of structural units A, B and C contained in each polymer chain within n [ ], p, q and r can be the same or different in each polymer chain within n [ ], p+q+r=1, p is 0 or more, q is 0 or more, r is 0 or more, if the polymer The molar content of each structural unit A, B and C contained in is set to p ^t , q ^t and r ^t respectively, then p ^t +q ^t +r ^t =1, p ^t is greater than 0, q ^t is greater than 0 , r ^t is greater than 0, X is a hydrogen atom or an organic group with 1 to 30 carbon atoms, Y is a 1-6 valent organic group with 1 to 30 carbon atoms derived from a monofunctional or difunctional or higher-functional thiol group-containing compound. , A represents the structural unit represented by the aforementioned formula (NB), and B contains at least one structural unit selected from the structural unit represented by the aforementioned formula (1-2) and the structural unit represented by the aforementioned formula (1-3). , C represents the structural unit represented by the aforementioned formula (AD), and there are a plurality of A's, B's, and C's which may be the same or different. For example, the polymer of claim 12 has a structure represented by formula (P4), In formula (P4), n is an integer from 1 to 6, p, q, r and s represent the molar content of structural units A, B, C and D contained in each polymer chain within n [ ] rate, p, q, r and s can be the same or different in each polymer chain within n [ ], p+q+r+s=1, p is 0 or more, q is 0 or more, r is 0 or more, s is 0 or more, if the molar content of each structural unit A, B, C and D contained in the polymer is respectively p ^t , q ^t , r ^t and s ^t , then p ^t +q ^t +r ^t +s ^t =1, p ^t is greater than 0, q ^t is greater than 0, r ^t is greater than 0, s ^t is greater than 0, X is a hydrogen atom or an organic group with 1 to 30 carbon atoms, Y is derived from A 1- to 6-valent organic group having a carbon number of 1 to 30 in a monofunctional or bifunctional or higher-functional thiol group-containing compound, A represents a structural unit represented by the aforementioned formula (NB), and B contains a member selected from the group consisting of the aforementioned formula (1-2 ) and at least one structural unit represented by the aforementioned formula (1-3), C represents the structural unit represented by the aforementioned formula (AD), D represents the structural unit represented by the aforementioned formula (MI) As for the structural unit, there are a plurality of A's, B's, C's and D's which may be the same or different. Such as the polymer of claim 1, wherein, The weight average molecular weight of this polymer is 2,000 or more and 20,000 or less. A polymer solution containing the polymer of any one of claims 1 to 15. The polymer solution of claim 16 further contains a multifunctional (meth)acrylic acid compound or a monofunctional (meth)acrylic acid compound or a combination thereof. The polymer solution of claim 16 is used for the formation of color filters, black matrices, spacers or partition materials. A photosensitive resin composition containing: The polymer of any one of claims 1 to 15; and Photoradical polymerization initiator. A hardened product formed from the photosensitive resin composition of claim 19. A polymer containing: a structural unit represented by formula (NB); a structural unit represented by formula (AD); and a structural unit represented by formula (MA), wherein, In the general formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2, In formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, In the formula (AD), R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. . Such as the polymer of claim 21, which further contains a structural unit represented by formula (MI), In the formula (MI), R ³¹ is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R ³² and R ³³ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. The polymer of claim 21, wherein the polymer has a structure represented by formula (P3'), In formula (P3'), n is an integer from 1 to 6, p, q' and r represent the molar content of structural units A, B' and C contained in each polymer chain within n [ ] , p, q' and r can be the same or different in each polymer chain within n [ ], p+q'+r=1, p is 0 or more, q' is 0 or more, r is 0 or more , if the molar content of each structural unit A, B and C contained in the polymer is set to p ^t , q ^t ' and r ^t respectively, then p ^t +q ^t '+r ^t =1, p ^t is greater than 0, ^{qt '} is greater than 0, rt is greater than 0, 30 is an organic group of 1 to 6 valence, A represents the structural unit represented by the aforementioned formula (NB), B' represents the structural unit represented by the aforementioned formula (MA), C represents the structural unit represented by the aforementioned formula (AD), There are a plurality of A's, B''s, and C's, which may be the same or different. The polymer of claim 22, wherein the polymer has a structure represented by formula (P4'), In formula (P4'), n is an integer from 1 to 6, p, q', r and s represent the structural units A, B', C and D contained in each polymer chain within n [ ]. Molar content, p, q', r and s can be the same or different in each polymer chain within n [ ], p+q'+r+s=1, p is 0 or more, q' is 0 or more, r is 0 or more, s is 0 or more, if the molar content of each structural unit A, B', C and D contained in the polymer is respectively set to p ^t , q ^t ', r ^t and s ^t , then p ^t +q ^t '+r ^t +s ^t =1, p ^t is greater than 0, q ^t ' is greater than 0, r ^t is greater than 0, s ^t is greater than 0, X is a hydrogen atom or carbon number 1 ~30 organic groups, Y is a 1-6 valent organic group with 1 to 30 carbon atoms derived from a monofunctional or bifunctional or higher-functional thiol group-containing compound, A represents the structural unit represented by the aforementioned formula (NB), B' represents the structural unit represented by the aforementioned formula (MA), C represents the structural unit represented by the aforementioned formula (AD), D represents the structural unit represented by the aforementioned formula (MI), and there are a plurality of A and B'. , C and D may be the same or different from each other. The polymer of claim 20, wherein, The softening point of this polymer is 60°C or more and 130°C or less.

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