Compound, polymer having unit derived from said compound, photosensitive resin composition containing said polymer, adhesive comprising said photosensitive resin composition, cured product obtained by curing said photosensitive resin composition, and electronic device provided with said cured product

Abstract

The purpose of the present disclosure is to provide a compound capable of providing a polymer having both good thermal stability and compatibility, a polymer having a unit derived from the compound, a photosensitive resin composition containing the polymer, an adhesive comprising the photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, and an electronic device provided with the cured product. The present disclosure relates to a compound represented by general formula (1).

Description

Compound, polymer having units derived from said compound, photosensitive resin composition containing said polymer, adhesive comprising said photosensitive resin composition, cured product obtained by curing said photosensitive resin composition, and electronic device comprising said cured product

[0001] The present disclosure relates to a compound, a polymer having units derived from the compound, a photosensitive resin composition containing the polymer, an adhesive made of the photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, and an electronic device including the cured product.

[0002] In general, electronic components such as semiconductor integrated circuits and flat panel displays (FPDs) are provided with protective films for preventing deterioration and damage, planarizing films for planarizing the device surface, and interlayer insulating films for insulating between wirings arranged in layers, and photosensitive resin compositions have been used to form these films. Photosensitive resin compositions are also used in a wide range of applications, such as as adhesives.

[0003] In Patent Document 1, a polymer having units derived from a norbornene monomer (BTHB-NB) represented by the following formula (BTHB-NB polymer) is used as the polymer (resin) to be blended into the photosensitive resin composition, and in Patent Document 2, a polymer containing units derived from a norbornene monomer (BTHB-NB) represented by the following formula and units derived from a norbornene monomer having a polyethylene glycol chain in its side chain (PEG-NB) is used, suggesting that UV transmittance, developability, and adhesiveness (adhesion) are improved.

[0004] Patent No. 6477492 Patent No. 6702194

[0005] The present inventors have prepared various photosensitive resin compositions using a BTHB-NB polymer, and have newly discovered that the BTHB-NB polymer requires improvement in compatibility with naphthoquinone diazide group-containing compounds, crosslinking agents, etc.

[0006] The present disclosure aims to provide a compound capable of providing a polymer having both good thermal stability and good compatibility, a polymer having units derived from the compound, a photosensitive resin composition containing the polymer, an adhesive made of the photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, and an electronic device including the cured product.

[0007] As a result of extensive investigations, the present inventors have found that a specific compound can provide a polymer having both good thermal stability and good compatibility, and have completed the present disclosure. That is, the present disclosure (1) relates to a compound represented by the following general formula (1): (In the general formula (1), n ​​is 0, 1 or 2, and R １ ~R ４ are each independently a monovalent substituent, and R １ ~R ４ At least one of the above is a group represented by the following formula (a): (In the general formula (a), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different.)

[0008] The present disclosure (2) relates to the compound according to the present disclosure (1), wherein the group represented by the formula (a) is a group represented by the following formula (a-1): (In general formula (a-1), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different.)

[0009] The present disclosure (3) relates to a compound represented by the general formula (a-1), wherein R５ is an alkylene group which may have a single bond, a linear, branched or cyclic structure.

[0010] The present disclosure (4) relates to a compound having two CF in the general formula (a). ｍ Cl （３－ｍ） Both are CF ２ The present invention relates to a compound according to any one of the present disclosures (1) to (3), wherein the compound is Cl.

[0011] The present disclosure (5) relates to the compound according to the present disclosure (1), which is a compound represented by the following formula:

[0012] The present disclosure (6) relates to a polymer having a unit derived from a compound represented by the following general formula (1): (In the general formula (1), n ​​is 0, 1 or 2, and R １ ~R ４ are each independently a monovalent substituent, and R １ ~R ４ At least one of the above is a group represented by the following formula (a): (In the general formula (a), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different.)

[0013] The present disclosure (7) relates to the polymer according to the present disclosure (6), wherein the group represented by the formula (a) is a group represented by the following formula (a-1): (In general formula (a-1), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. * is a bond. Two CF ｍ Cl（３－ｍ） may be the same or different.)

[0014] The present disclosure (8) is a compound represented by the general formula (a-1), wherein R ５ is an alkylene group which may have a single bond, a linear, branched or cyclic structure.

[0015] The present disclosure (9) relates to a compound having two CF in the general formula (a). ｍ Cl （３－ｍ） Both are CF ２ The polymer according to any one of the present disclosure (6) to (8), wherein the aryl group is Cl.

[0016] The present disclosure (10) relates to the polymer according to the present disclosure (6), wherein the compound represented by the general formula (1) is a compound represented by the following formula:

[0017] The present disclosure (11) relates to a photosensitive resin composition containing the polymer according to any one of the present disclosures (6) to (10).

[0018] The present disclosure (12) relates to the photosensitive resin composition according to the present disclosure (11), further comprising a naphthoquinone diazide group-containing compound.

[0019] The present disclosure (13) relates to the photosensitive resin composition according to the present disclosure (11), further comprising a crosslinking agent and a photopolymerization initiator.

[0020] The present disclosure (14) relates to an adhesive comprising the photosensitive resin composition according to any one of the present disclosures (11) to (13).

[0021] The present disclosure (15) relates to a cured product obtained by curing the photosensitive resin composition according to any one of the present disclosures (11) to (13).

[0022] The present disclosure (16) relates to an electronic device comprising the cured product according to the present disclosure (15).

[0023] The present disclosure (17) relates to the electronic device according to the present disclosure (16), wherein the cured product is an adhesive layer, a protective film, an insulating film, and / or a planarizing film.

[0024] The present disclosure (18) relates to the electronic device according to the present disclosure (16), which is a semiconductor device including a stacked semiconductor element, the stacked semiconductor element having a plurality of semiconductor elements and the cured material provided between the semiconductor elements and bonding them together.

[0025] The present disclosure (19) relates to the electronic device according to the present disclosure (16), which includes an optical filter having the cured product.

[0026] The present disclosure (20) relates to an electronic device according to the present disclosure (19) that includes a solid-state imaging element having the optical filter.

[0027] The present disclosure (21) relates to the electronic device according to the present disclosure (19), which is an image display device including the optical filter.

[0028] The present disclosure (22) relates to a compound represented by the following general formula (10): (In general formula (10), R １１ ~R １４ are each independently a monovalent substituent, and R １１ ~R １４ At least one of the above is a group represented by the following formula (a-1): (In general formula (a-1), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different.)

[0029] The present disclosure (23) is a compound represented by the general formula (a-1), wherein R ５ is an alkylene group which may have a single bond, a linear, branched or cyclic structure.

[0030] The present disclosure (24) relates to a compound represented by the general formula (a-1), in which two CF ｍ Cl （３－ｍ） Both are CF ２ The present disclosure relates to the compound according to (22) or (23), wherein the compound is Cl.

[0031] The present disclosure (25) relates to the compound according to the present disclosure (22), which is a compound represented by the following formula:

[0032] The compound of the present disclosure is a compound represented by the general formula (1) above, and therefore can provide a polymer having both good thermal stability and good compatibility.

[0033] The polymer of the present disclosure is a polymer having units derived from the compound represented by the general formula (1), and therefore has good thermal stability and compatibility.

[0034] The photosensitive resin composition of the present disclosure contains the polymer of the present disclosure, and therefore has good thermal stability and is excellent in various performances (for example, it can be applied evenly to a substrate and can draw a uniform exposure pattern on the entire substrate).

[0035] The adhesive of the present disclosure is made from the photosensitive resin composition of the present disclosure, and therefore has good thermal stability and excellent performance (for example, it is possible to form a uniform adhesive body without defects, etc., and therefore adhesive strength can be easily increased).

[0036] The cured product of the present disclosure is obtained by curing the photosensitive resin composition of the present disclosure, and therefore has good thermal stability and excellent performance (for example, excellent transparency without scattering because a uniform cured product without defects can be formed).

[0037] The electronic device of the present disclosure includes the cured product of the present disclosure, and therefore has good thermal stability and excellent performance (for example, since the cured product is uniform, there is no individual difference, and good yield and performance).

[0038] Fig. 1 is a cross-sectional view showing an example of an electronic device according to the present disclosure. Fig. 2 is a cross-sectional view showing an example of an electronic device according to the present disclosure. Fig. 3 is a cross-sectional view showing an example of an electronic device according to the present disclosure. Fig. 4 is a cross-sectional view showing an example of an electronic device according to the present disclosure. Fig. 5 is a photograph of the surface of a coating film 3 obtained in Example 3, observed under a microscope. Fig. 6 is a photograph of the surface of a coating film 10 obtained in Comparative Example 3, observed under a microscope.

[0039] The present disclosure will be described in detail below, but the following description of the constituent elements is an example of an embodiment of the present disclosure, and the present disclosure is not limited to these specific details. Various modifications can be made within the scope of the gist of the present disclosure.

[0040] In this specification, unless otherwise specified, the expression "X to Y" in the description of a numerical range means at least X and at most Y. For example, "1 to 5% by mass" means "at least 1% by mass and at most 5% by mass."

[0041] In this specification, the terms "polymer," "resin," and "polymeric substance" are synonymous and mean a polymeric compound unless otherwise noted.

[0042] The compound of the present disclosure is a compound represented by the general formula (1), and therefore can provide a polymer having both excellent thermal stability and compatibility. By using the compound of the present disclosure, a polymer having excellent compatibility can be provided while the excellent properties (e.g., thermal stability) of the norbornene skeleton are sufficiently ensured.

[0043] In the present disclosure, the reason why the above-mentioned effects are obtained is not necessarily clear, but it is presumed that the following mechanism is involved: ｍ Cl （３－ｍ） (monochlorodifluoromethyl group (-CF ２ Cl) and dichloromonofluoromethyl group (-CFCl ２ )) CF ｍ Cl （３－ｍ） is a trifluoromethyl group (-CF ３ ), the hydrophilicity is similarly low, but the lipophilicity is good, so that a polymer with excellent compatibility can be provided. ｍ Cl （３－ｍ） Since this does not significantly reduce the thermal stability, which is an excellent property of the norbornene skeleton, a polymer having good thermal stability can be provided.

[0044] The polymer of the present disclosure has both good thermal stability and compatibility. In particular, the polymer of the present disclosure has excellent compatibility with naphthoquinone diazide group-containing compounds blended in positive-type photosensitive resin compositions and with crosslinking agents blended in negative-type photosensitive resin compositions. Therefore, whether the polymer is used in a positive-type or negative-type photosensitive resin composition, the components in the composition can be well dispersed. Therefore, adhesives and cured products using the photosensitive resin composition have excellent performance and can be used in a wide range of applications.

[0045] The polymer of the present disclosure is highly soluble in alkalis and organic solvents, and a composition containing the polymer of the present disclosure can be patterned by controlling the solubility through a photoreaction.

[0046] (Compound) The compound of the present disclosure is a compound represented by the following general formula (1). (In the general formula (1), n ​​is 0, 1 or 2, and R １ ~R ４ are each independently a monovalent substituent, and R １ ~R ４ At least one of the above is a group represented by the following formula (a): (In the general formula (a), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different.)

[0047] When the compound represented by the general formula (1) has a plurality of groups represented by the formula (a), the groups represented by the formula (a) may be the same or different.

[0048] In formula (1), n ​​is 0, 1, or 2, preferably 0 or 1, and more preferably 0. This tends to more suitably achieve the effects of the present disclosure.

[0049] In formula (1), R １ ~R ４ The monovalent substituent other than the group represented by formula (a) is not particularly limited as long as it is a monovalent group other than the group represented by formula (a), and examples thereof include a hydrogen atom, a monovalent organic group, a halogen atom, a hydroxyl group, a nitro group, and a carboxyl group. Among these, a hydrogen atom and a monovalent organic group are preferred, and a hydrogen atom is more preferred. １ ~R ４ The monovalent organic group is a monovalent organic group other than the group represented by formula (a). In this specification, the organic group means a group having one or more carbon atoms.

[0050] R １ ~R ４ The monovalent organic group R is not particularly limited as long as it is a monovalent group having one or more carbon atoms. １ ~R ４ The monovalent organic group preferably has 1 to 30 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.

[0051] R １ ~R ４ Examples of the monovalent organic group include a monovalent hydrocarbon group.

[0052] R １ ~R ４ The monovalent organic group (preferably a monovalent hydrocarbon group) may have a heteroatom. Examples of the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a phosphorus atom, and a silicon atom. １ ~R ４ The monovalent organic group (preferably a monovalent hydrocarbon group) may have a plurality of these heteroatoms.

[0053] Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, a cycloalkyl group, a heterocyclic group, etc. Among these, an alkyl group is preferred.

[0054] Examples of the alkyl group may be linear or branched, and include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. Since the alkyl group may be linear or branched, a propyl group means an n-propyl group or an isopropyl group, and a butyl group means an n-butyl group, a sec-butyl group or a tert-butyl group, and the same applies to other groups that may be linear or branched.

[0055] The alkenyl group may be, for example, linear or branched, and includes a vinyl group, an allyl group, a propenyl group, a methylethenyl group, and the like.

[0056] The alkynyl group may be, for example, linear or branched, and includes an ethynyl group, a propargyl group, and the like.

[0057] The alkylidene group may be, for example, linear or branched, and includes a methylidene group, an ethylidene group, and the like.

[0058] Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0059] Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0060] Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

[0061] Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

[0062] The monovalent hydrocarbon group may have a heteroatom, and may be an alkoxy group or a group represented by -C(=O)-B (B represents a hydrogen atom or a monovalent organic group). In this specification, an alkoxy group is a group represented by -O-A (A represents an alkyl group), and the alkyl group of A is R １ ~R ４ The monovalent organic group of B is the same as the alkyl group of R, including preferred embodiments. １~R ４ The same applies to the monovalent organic group of the above, including preferred embodiments.

[0063] R １ ~R ４ a halogen atom, R １ ~R ４ Examples of the halogen atom that the monovalent organic group may have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0064] In formula (1), R １ ~R ４ At least one of R is a group represented by the formula (a). １ ~R ４ may all be groups represented by the formula (a), but １ ~R ４ Among these, it is preferable that 1 to 3 are groups represented by the formula (a), it is more preferable that 1 to 2 are groups represented by the formula (a), and it is even more preferable that 1 is a group represented by the formula (a). １ ~R ４ Of the remaining groups other than the group represented by formula (a), it is preferred that at least one is a hydrogen atom, and it is more preferred that all are hydrogen atoms. １ ~R ４ When at least one of the groups is a hydrogen atom, the light transmittance of the resulting cured product tends to be further improved.

[0065] In general formula (a), R ５ represents a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester (-C(=O)-O-), a carbonyl (-C(=O)-), an ether (-O-), an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. X represents a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom.

[0066] R ５The number of carbon atoms in the alkylene group, which may have a linear, branched, or cyclic structure, is preferably 1 to 30, more preferably 1 to 15, even more preferably 1 to 8, particularly preferably 1 to 3, and most preferably 1 or 2. This tends to more suitably achieve the effects of the present disclosure.

[0067] R ５ Examples of the alkylene group include a methylene group, an ethylene group, a propylene group such as a 1,3-propylene group or a 1,2-propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, a tetradecamethylene group, a pentadecamethylene group, a hexadecamethylene group, a heptadecamethylene group, an octadecamethylene group, a nonadecamethylene group, an insalen group, a 1-methyl-1,3-propylene group, a 2-methyl-1,3-propylene group, a 2-methyl-1,2-propylene group, a 1-methyl-1,4-butylene group, a 2- Examples of such hydrocarbon groups include saturated chain hydrocarbon groups such as methyl-1,4-butylene, methylidene, ethylidene, propylidene, and 2-propylidene; monocyclic hydrocarbon ring groups such as cycloalkylene groups having 3 to 10 carbon atoms, including cyclobutylene groups such as 1,3-cyclobutylene, cyclopentylene groups such as 1,3-cyclopentylene, cyclohexylene groups such as 1,4-cyclohexylene, and cyclooctylene groups such as 1,5-cyclooctylene; and crosslinked cyclic hydrocarbon ring groups such as bicyclic to tetracyclic hydrocarbon ring groups, including norbornylene groups such as 1,4-norbornylene and 2,5-norbornylene, and adamantylene groups such as 1,5-adamantylene and 2,6-adamantylene. Of these, saturated chain hydrocarbon groups are preferred, and linear saturated chain hydrocarbon groups are more preferred.

[0068] R ５ Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring.

[0069] R ５ The amide has a structure represented by (-C(=O)NA-) (A represents a hydrogen atom or a monovalent organic group), and examples thereof include -C(=O)NH- and -C(=O)NCH ３-, etc. Examples of the monovalent organic group of A include R １ ~R ４ The same applies to the monovalent organic group of the above, including preferred embodiments.

[0070] R ５ The amine has a structure represented by (-NB-) (B represents a hydrogen atom or a monovalent organic group), for example, -NH-, -NCH ３ -, etc. Examples of the monovalent organic group of B include R １ ~R ４ The same applies to the monovalent organic group of the above, including preferred embodiments.

[0071] R ５ is more preferably an alkylene group which may have a linear, branched or cyclic structure, or a single bond.

[0072] X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom, preferably a hydroxyl group. When the terminal of the side chain is a hydroxyl group, it tends to be possible to more suitably provide a polymer that can have properties such as water repellency, adhesion, and alkali solubility. When the terminal of the side chain is an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, or an oxycarboxy group, it tends to be possible to more suitably provide a polymer that can have properties such as water repellency, water resistance, and polarity conversion by acid or the like. When the terminal of the side chain is a hydrogen group, it tends to be possible to more suitably provide a polymer that can have properties such as water repellency and water resistance.

[0073] The oxycarbonyl group of X is a group represented by (—O—C(═O)A) (A represents a hydrogen atom or a monovalent organic group), for example, —O—C(═O)CH ３ The monovalent organic group of A is R １ ~R ４ The same applies to the monovalent organic group of the above, including preferred embodiments.

[0074] The oxysulfonyl group of X is (—O—SO ２ -A) (A represents a hydrogen atom or a monovalent organic group), for example, —O—SO ２ -CH ３ The monovalent organic group of A is R １ ~R４ The same applies to the monovalent organic group of the above, including preferred embodiments.

[0075] The oxycarboxy group of X is a group represented by (—O—C(═O)—O—A) (A represents a hydrogen atom or a monovalent organic group), for example, —O—C(═O)—O—CH ３ , -OC(=O)-OC(CH ３ ) ３ The monovalent organic group of A is R １ ~R ４ and the monovalent organic group, including preferred embodiments, except that "the number of carbon atoms in the monovalent organic group is preferably 1 to 30, more preferably 1 to 8, and even more preferably 1 to 4."

[0076] In the general formula (a), two CF ｍ Cl （３－ｍ） may be the same or different. That is, two CF ｍ Cl （３－ｍ） is one monochlorodifluoromethyl group (-CF ２ Cl, m=2) and one dichloromonofluoromethyl group (-CFCl ２ , m=1), and two CFs ｍ Cl （３－ｍ） are both monochlorodifluoromethyl groups (-CF ２ Cl, m=2), and two CF ｍ Cl （３－ｍ） Both are dichloromonofluoromethyl groups (-CFCl ２ , m=1). Among them, two CFs ｍ Cl （３－ｍ） Both are -CF ２ Preferably it is Cl.

[0077] As described above, the group represented by the formula (a) is preferably a group represented by the following formula (a-1), and in the following formula (a-1), R ５ However, it is more preferably an alkylene group which may have a linear, branched or cyclic structure, or a single bond. (In general formula (a-1), m is 1 or 2, and R ５is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different. In general formula (a-1), m, R ５ represents m and R in general formula (a). ５ (Similar to the above.)

[0078] The compound represented by the general formula (1) is most preferably a compound represented by the following formula:

[0079] (Method for producing the compound represented by the general formula (1)) Next, a method for producing the compound represented by the general formula (1) will be described. First, a compound represented by the following general formula (10) is prepared. The compound represented by the following general formula (10) is an important intermediate for producing the compound represented by the general formula (1).

[0080] (In general formula (10), R １１ ~R １４ are each independently a monovalent substituent, and R １１ ~R １４ At least one of the following is a group represented by the following formula (a-1): １１ ~R １４ represents R in general formula (1). １ ~R ４ (Similar to the above.) (In general formula (a-1), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different. General formula (a-1) is the same as the above-mentioned general formula (a-1).

[0081] The compound represented by the general formula (10) is most preferably a compound represented by the following formula:

[0082] For example, the compound represented by the general formula (10) can be obtained by carrying out the following Ene reaction (reaction shown in the following formula (10-1)). The reactions in the following brackets [ ] react in concert. In the following formula (10-1), CF ｍ Cl （３－ｍ） is CF ２ The case of Cl was explained, but CF ｍ Cl （３－ｍ） is CF ２ In the case of other than Cl, the same reaction proceeds. (In formula (10-1), R ５’ represents R in general formula (a). ５ is a monovalent group corresponding to

[0083] Examples of the substrate (the compound on the right side of the reaction raw materials in the formula (10-1)) in the reaction shown in formula (10-1) include propylene, 1-butene, 2-methylpropene, 1-pentene, 3-methyl-1-butene, and allylbenzene.

[0084] The reaction represented by the formula (10-1) may be carried out under pressure as needed, and the reaction conditions are preferably 20 to 200° C. for 2 to 70 hours.

[0085] The product produced by the reaction shown in formula (10-1) is a compound having one group represented by formula (a-1). By using this product as a substrate (the compound on the right side of the reaction raw materials in the formula) in the reaction shown in formula (10-1), a compound having two groups represented by formula (a-1) is obtained by the reaction shown in formula (10-1). By using this product as a substrate (the compound on the right side of the reaction raw materials in the formula) in the reaction shown in formula (10-1), a compound having three groups represented by formula (a-1) is obtained by the reaction shown in formula (10-1). By using this product as a substrate (the compound on the right side of the reaction raw materials in the formula) in the reaction shown in formula (10-1), a compound having four groups represented by formula (a-1) is obtained by the reaction shown in formula (10-1).

[0086] The reaction product may be separated and purified by a conventional method such as concentration, distillation, extraction, recrystallization, filtration, chromatographic separation, etc., and two or more of these methods may be used in combination.

[0087] By the above steps, the compound represented by the general formula (10) can be produced. The compound represented by the general formula (10) can be synthesized using a Grignard reagent and a ketone. In the following formula (10-2), CF ｍ Cl （３－ｍ） is CF ２ The case of Cl was explained, but CF ｍ Cl （３－ｍ） is CF ２ A similar reaction proceeds in the case of an alkyl group other than Cl. In addition, a compound having a plurality of groups represented by formula (a-1) can also be produced by sequentially reacting them in the same manner as in the reaction represented by formula (10-1). (In formula (10-2), R ５’ represents R in general formula (a). ５ is a monovalent group corresponding to

[0088] Through the above steps, the compound represented by the general formula (10) can be prepared.

[0089] Next, the compound represented by the general formula (10) is reacted with a cyclic diene such as cyclopentadiene. This reaction forms a norbornene skeleton. As a result, a compound in which n is 0 in formula (1) is obtained. By using this product as a substrate in the reaction, a compound in which n is 1 in formula (1) is obtained. By using this product as a substrate in the reaction, a compound in which n is 2 in formula (1) is obtained. Note that cyclopentadiene that has been previously purified by distillation may be used, or cyclopentadiene generated by thermal decomposition in the reaction system may be used.

[0090] The reaction of the compound represented by the general formula (10) with a cyclic diene such as cyclopentadiene may be carried out under pressure, if necessary, and the reaction conditions are preferably 0 to 200°C for 2 to 200 hours.

[0091] The reaction product may be separated and purified by a conventional method such as concentration, distillation, extraction, recrystallization, filtration, chromatographic separation, etc., and two or more of these methods may be used in combination.

[0092] Through the above steps, compounds represented by the general formula (1) in which X is a hydroxyl group can be obtained. Compounds in which X is other than a hydroxyl group can be produced appropriately by those skilled in the art.

[0093] For example, a compound in which X is an alkoxy group can be produced by subjecting a compound in which X is a hydroxyl group to a nucleophilic substitution reaction with an alcohol to synthesize an ether.

[0094] Furthermore, for example, a compound in which X is a hydrogen atom can be produced by a method in which the hydroxyl group of a compound in which X is a hydroxyl group is halogenated and the halogen is reduced (with zinc or the like).

[0095] Furthermore, for example, a compound in which X is an oxycarbonyl group can be produced by subjecting a compound in which X is a hydroxyl group to Fischer esterification with a corresponding carboxylic acid, esterification using a condensing agent such as a carbodiimide, reaction with a corresponding carboxylic acid anhydride under acidic or basic conditions, reaction with a corresponding carboxylic acid halide under basic conditions, or the like.

[0096] Furthermore, for example, a compound in which X is an oxysulfonyl group can be produced by reacting a compound in which X is a hydroxyl group with the corresponding sulfonic acid anhydride under basic conditions, or with the corresponding sulfonic acid halide under basic conditions.

[0097] Furthermore, for example, a compound in which X is an oxycarboxy group can be produced by reacting a compound in which X is a hydroxyl group with the corresponding dicarbonic anhydride under basic conditions, or with the corresponding carbonic acid halide under basic conditions.

[0098] The products after these reactions may be separated and purified by conventional methods, such as concentration, distillation, extraction, recrystallization, filtration, chromatographic separation, etc., and two or more of these methods may be used in combination.

[0099] Through the above steps, the compound represented by the general formula (1) can be prepared.

[0100] (Polymer) The polymer of the present disclosure is a polymer having units derived from the compound represented by the general formula (1). In the polymer of the present disclosure, the units derived from the compound represented by the general formula (1) may be the same or different. Therefore, the polymer of the present disclosure may be a polymer having one or more types of units corresponding to the units derived from the compound represented by the general formula (1). In the polymer of the present disclosure, it is preferable that the units derived from the compound represented by the general formula (1) are the same.

[0101] The polymer of the present disclosure may have, in addition to the units derived from the compound represented by general formula (1), units other than the units derived from the compound represented by general formula (1) (other units). Examples of other units include units derived from a compound represented by the following general formula (3), maleic anhydride, maleimides, α-haloacrylates, α-trihalomethylacrylates, etc. The other units may be used alone or in combination of two or more. (In the general formula (3), n is 0, 1 or 2, and R １ ~R ４ are each independently a monovalent substituent, and R １ ~R ４is not a group represented by the formula (a). １ ~R ４ is R １ ~R ４ is not a group represented by formula (a), except that n and R １ ~R ４ It is the same as:

[0102] Examples of the compound represented by the general formula (3) include norbornene (bicyclo[2.2.1]-hept-2-ene), compounds having an alkyl group such as 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, and 5-decyl-2-norbornene, and compounds having an alkenyl group such as 5-allyl-2-norbornene and 5-(2-propenyl)-2-norbornene. , 5-(1-methyl-4-pentenyl)-2-norbornene, etc., those having an alkynyl group include 5-ethynyl-2-norbornene, etc., those having an aralkyl group include 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, etc., and those having a haloalkyl group include 5-perfluorobutyl-2-norbornene, 5-(2-hydroxy-2,2-bistrifluoromethyl)ethyl-2-norbornene, etc. Of these, norbornene is preferred.

[0103] When the polymer of the present disclosure is a copolymer having, in addition to the unit derived from the compound represented by general formula (1), a unit other than the unit derived from the compound represented by general formula (1), the polymer may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer.

[0104] In the polymer of the present disclosure, the content of units derived from the compound represented by the general formula (1) is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 60 mol% or more, particularly preferably 80 mol% or more, most preferably 90 mol% or more, and even most preferably 95 mol% or more, based on 100 mol% of the polymer. This tends to more favorably achieve the effects of the present disclosure. In this specification, the content of each unit in the polymer is measured by the method described in the Examples.

[0105] The weight average molecular weight (Mw) of the polymer of the present disclosure is preferably 3,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 100,000. This tends to more suitably obtain the effects of the present disclosure.

[0106] The dispersity (Mw / Mn) of the polymer of the present disclosure is preferably 1.05 to 3.00, more preferably 1.05 to 2.50, and even more preferably 1.05 to 2.00. This tends to more favorably achieve the effects of the present disclosure. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer are measured by the method described in the examples.

[0107] The polymer of the present disclosure is a polymer having units derived from the compound represented by the general formula (1), and the units derived from the compound represented by the general formula (1) are formed by synthesis using the compound represented by the general formula (1) as a monomer.

[0108] The polymerization method for the polymer of the present disclosure is not particularly limited, and a conventional polymerization reaction can be used. Known polymerization methods using a monomer having a norbornene skeleton include addition polymerization and ring-opening polymerization (ring-opening metathesis polymerization). Therefore, a person skilled in the art can appropriately produce the polymer of the present disclosure by a known polymerization method using the above-mentioned monomers, with reference to, for example, methods described in Japanese Patent No. 6477492, Japanese Patent No. 6702194, and metathesis polymerization described in Kobunshi, Vol. 41, February issue (1992), pp. 86-89. The polymerization reaction in the polymerization is not particularly limited, and may be any of a radical polymerization reaction, a coordination polymerization reaction, a cationic polymerization reaction, and an anionic polymerization reaction. Of these, a radical polymerization reaction or a coordination polymerization reaction is preferred. Furthermore, addition polymerization and ring-opening polymerization (ring-opening metathesis polymerization) are preferred as the polymerization method.

[0109] It is well known that in polymerization using a monomer having a norbornene skeleton, the structure of the polymer obtained varies depending on the polymerization method. For example, when a polymer is produced by addition polymerization using a compound represented by the general formula (1) as the monomer, a polymer having a unit (repeating unit) represented by the following general formula (11) is obtained. On the other hand, when a polymer is produced by ring-opening metathesis polymerization using a compound represented by the general formula (1) as the monomer, a polymer having a unit (repeating unit) represented by the following general formula (12) is obtained. Furthermore, a polymer having a unit represented by the following general formula (12) is converted into a polymer having a unit (repeating unit) represented by the following general formula (13) by hydrogenation. As described above, examples of units derived from the compound represented by the general formula (1) include a unit represented by the following general formula (11), a unit represented by the following general formula (12), and a unit represented by the following general formula (13). Here, the polymer of the present disclosure does not usually have a unit represented by the following general formula (11) as well as a unit represented by the following general formula (12) or a unit represented by the following general formula (13). This is because the polymerization methods are different. On the other hand, a polymer having a unit represented by the following general formula (12) becomes a polymer having a unit represented by the following general formula (13) upon hydrogenation, and therefore the polymer of the present disclosure may have a unit represented by the following general formula (13) in addition to a unit represented by the following general formula (12). The ratio of both units can be appropriately adjusted by changing the conditions for hydrogenation. The polymer of the present disclosure is preferably a polymer obtained by addition polymerization, specifically a polymer having a unit represented by the following general formula (11). (In general formula (11), n, R １ ~R ４ represents n and R in general formula (1). １ ~R ４ (Similar to the above.) (In general formula (12), n, R １ ~R ４ represents n and R in general formula (1). １ ~R ４ (Similar to the above.) (In general formula (13), n, R １ ~R ４represents n and R in general formula (1). １ ~R ４ (Similar to the above.)

[0110] As described above, in the polymer of the present disclosure, the units derived from the compound represented by the general formula (1) may be the same or different. Therefore, the units represented by the general formula (11), the units represented by the general formula (12), and the units represented by the general formula (13) may also be the same or different. The polymer of the present disclosure may be a polymer having one or more units corresponding to the unit represented by the general formula (11). The polymer of the present disclosure may also be a polymer having one or more units corresponding to the unit represented by the general formula (12). The polymer of the present disclosure may also be a polymer having one or more units corresponding to the unit represented by the general formula (13). The polymer of the present disclosure may also be a polymer having one or more units corresponding to the unit represented by the general formula (12) and one or more units corresponding to the unit represented by the general formula (13). In the polymer of the present disclosure, it is preferable that the units in the repeating units are the same.

[0111] (Method for Producing Polymer) The polymer of the present disclosure can be produced, for example, as follows.

[0112] <Polymerization step 1 (addition polymerization)> First, a compound represented by the general formula (1) is prepared as a monomer. Examples of the compound represented by the general formula (1) include compounds represented by the following formula:

[0113] Next, the compound represented by the general formula (1) is subjected to addition polymerization. Here, for example, a polymer of the compound represented by the general formula (1) is formed by radical polymerization. The compound represented by the general formula (1) and a polymerization initiator are dissolved in a solvent, and then heated for a predetermined time, thereby solution-polymerizing the compound represented by the general formula (1). The heating temperature is, for example, 50 to 80°C, and the heating time is 10 to 20 hours.

[0114] Examples of the solvent include diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, etc. These may be used alone or in combination of two or more.

[0115] The polymerization initiator is not particularly limited as long as it allows the polymerization reaction to proceed, and examples of the polymerization initiator include azo compounds, peroxide compounds, and redox compounds. These may be used alone or in combination of two or more.

[0116] Examples of azo compounds include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN).

[0117] Examples of peroxide compounds include t-butyl peroxypivalate, di-t-butyl peroxide, i-butyryl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnamyl peroxide, di-n-propyl peroxydicarbonate, t-butyl peroxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide, and ammonium persulfate.

[0118] Examples of redox compounds are used in combination of an oxidizing agent and a reducing agent, and examples of the oxidizing agent include hydrogen peroxide, persulfate, and cumene hydroperoxide, while examples of the reducing agent include iron (II) ion salts, copper (I) ion salts, ammonia, and triethylamine.

[0119] The amount (number of moles) of the polymerization initiator is preferably 1 to 10% of the number of moles of the compound represented by the general formula (1). By appropriately setting the amount of the polymerization initiator within the above range and appropriately setting the reaction temperature and reaction time, the molecular weight of the resulting polymer can be adjusted.

[0120] Polymerization step 1 can polymerize a polymer having a unit represented by general formula (11). The solution or dispersion containing the obtained polymer is appropriately purified according to a known method and dried to obtain the polymer of the present disclosure. Examples of purification methods include extraction, chromatographic separation, reprecipitation, filtration, and distillation by heating under reduced pressure.

[0121] In the above explanation, a case where a polymer having units derived from the compound represented by the general formula (1) is formed by radical polymerization has been described. However, when a polymer having units derived from the compound represented by the general formula (1) is formed by coordination polymerization, an organometallic catalyst may be used instead of a polymerization initiator. Other conditions may be the same as those for radical polymerization. This allows polymerization of a polymer having units represented by the general formula (11). It is preferable to form a polymer having units derived from the compound represented by the general formula (1) by addition polymerization.

[0122] The organometallic catalyst is not particularly limited as long as it allows the addition polymerization to proceed, but for example, a phosphine-based ligand may be coordinated to a palladium complex to form a counter anion, etc. These may be used alone or in combination of two or more kinds.

[0123] Examples of palladium complexes include palladium chloride (PdCl ２ ), palladium acetate (Pd(OAc) ２ ), tetrakistriphenylphosphine palladium (Pd(PPh ３ ) ４ ), dichlorobistriphenylphosphine palladium (Pd(PPh ３ ) 2Cl ２ ), palladium nitrate, bisacetonitriledichloropalladium, bisbenzonitriledichloropalladium, bisacetylacetonatepalladium, bisdibenzylideneacetonepalladium (Pd(dba) ２ ), trisdibenzylideneacetonedipalladium (Pd ２ (dba) ３ ), bisdiphenylphosphinoferrocenedichloropalladium (PdCl２ (dppf)), dichlorobisdi-t-butyl-p-dimethylaminophenylphosphinopalladium, di-μ-chlorobis-η-allylpalladium, and the like.

[0124] Examples of phosphine-based ligands include triphenylphosphine (PPh ３ ), tricyclohexylphosphine (PCy ３ ), tri(t-butyl)phosphine (P(tBu) ３ ), tri(o-tolyl)phosphine (P(o-Tolyl) ３ ), 1,1'-bis(diphenylphosphino)ferrocene (dppf), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dpppp), 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos), 2-(di-tert-butylphosphino)biphenyl (JohnPhos), 2-(dicyclohexylphosphino)-2'-(dimethylamino)biphenyl (DavePhos), 4,5'-bis(diphenylphosphino)-9,9'-dimethylxanthene (XantPhos), and the like.

[0125] Examples of counter anions include triphenylmethylium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(2,4,6-trifluorophenyl)borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diphenylanilinium tetrakis(pentafluorophenyl)borate, and lithium tetrakis(pentafluorophenyl)borate.

[0126] The amount (number of moles) of the organometallic catalyst is preferably 0.01 to 10% of the number of moles of the compound represented by the general formula (1). By appropriately setting the amount of the organometallic catalyst within the above range and appropriately setting the reaction temperature and reaction time, the molecular weight of the resulting polymer can be adjusted.

[0127] <Polymerization Step 2 (Ring-Opening Metathesis Polymerization)> Polymerization Step 2 (Ring-Opening Metathesis Polymerization) is significantly different from polymerization Step 1 (Addition Polymerization) in that a metathesis polymerization catalyst is used instead of a polymerization initiator. Other conditions and the like may be the same as those of polymerization Step 1 (Addition Polymerization).

[0128] A metathesis polymerization catalyst is a complex formed by bonding a plurality of ions, atoms, polyatomic ions, and / or compounds to a transition metal atom as a central atom. A single metathesis polymerization catalyst may be used, or two or more types may be used in combination. The transition metal atom is an atom of Groups 5, 6, or 8 of the long-form periodic table. The atom of each group is not particularly limited. Examples of Group 5 atoms include tantalum, Group 6 atoms include molybdenum and tungsten, and Group 8 atoms include ruthenium and osmium. Among these, ruthenium and osmium are preferred, and ruthenium is more preferred.

[0129] As a complex having ruthenium as a central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferred. Here, "carbene compound" is a general term for compounds having a methylene free radical, and means a compound having an uncharged divalent carbon atom (carbene carbon) represented by (>C:). Ruthenium carbene complexes are relatively stable against air and water and are not easily deactivated, making them easy to handle.

[0130] Specific examples of ruthenium carbene complexes include benzylidene(1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride, (1,3-dimesitylimidazolidin-2-ylidene)(3-methyl-2-buten-1-ylidene)(tricyclopentylphosphine)ruthenium dichloride, and benzylidene(1,3-dimesityl-octahydrobenzimidazol-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride. chloride, benzylidene[1,3-di(1-phenylethyl)-4-imidazolin-2-ylidene](tricyclohexylphosphine)ruthenium dichloride, benzylidene(1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride, benzylidene(tricyclohexylphosphine)(1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene) Ruthenium carbene complex compounds in which a heteroatom-containing carbene compound is bonded to a neutral electron donor compound, such as (1,3-diisopropylhexahydropyrimidin-2-ylidene)(ethoxymethylene)(tricyclohexylphosphine)ruthenium dichloride and benzylidene(1,3-dimesitylimidazolidin-2-ylidene)pyridine ruthenium dichloride; benzylidenebis(tricyclohexylphosphine)ruthenium dichloride, (3- Ruthenium carbene complex compounds in which two neutral electron donor compounds are bonded, such as methyl-2-buten-1-ylidene)bis(tricyclopentylphosphine)ruthenium dichloride; ruthenium carbene complex compounds in which two heteroatom-containing carbene compounds are bonded, such as benzylidenebis(1,3-dicyclohexylimidazolidin-2-ylidene)ruthenium dichloride and benzylidenebis(1,3-diisopropyl-4-imidazolin-2-ylidene)ruthenium dichloride;Examples include (1,3-dimesitylimidazolidin-2-ylidene)(phenylvinylidene)(tricyclohexylphosphine)ruthenium dichloride, (t-butylvinylidene)(1,3-diisopropyl-4-imidazolin-2-ylidene)(tricyclopentylphosphine)ruthenium dichloride, and bis(1,3-dicyclohexyl-4-imidazolin-2-ylidene)phenylvinylideneruthenium dichloride;

[0131] The amount (number of moles) of the metathesis polymerization catalyst is preferably 0.01 to 10% of the number of moles of the compound represented by the general formula (1). By appropriately setting the amount of the metathesis polymerization catalyst within the above range and appropriately setting the reaction temperature and reaction time, the molecular weight of the resulting polymer can be adjusted.

[0132] In this polymerization step 2, a polymer having a unit represented by the general formula (12) can be polymerized.

[0133] The polymer having the unit represented by the general formula (12) can be converted into a polymer having the unit represented by the general formula (13) by hydrogenation, if necessary.

[0134] The hydrogenation method and reaction conditions are not particularly limited, and hydrogenation may be carried out by a known method and under known conditions. Typically, hydrogenation is carried out at 20 to 150°C under a hydrogen pressure of 0.1 to 10 MPa in the presence of a hydrogenation catalyst. The hydrogenation rate can be freely selected by changing the amount of hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, the reaction time, etc. Typically, a compound containing any of the metals in Groups 4 to 11 of the Periodic Table can be used as the hydrogenation catalyst. For example, a compound containing a Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, or Pt atom can be used as the hydrogenation catalyst. More specific examples of the hydrogenation catalyst include metallocene compounds of Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, Re, etc.; supported heterogeneous catalysts in which metals such as Pd, Ni, Pt, Rh, Ru, etc. are supported on a carrier such as carbon, silica, alumina, diatomaceous earth, etc.; homogeneous Ziegler-type catalysts in which an organic salt or acetylacetone salt of a metal element such as Ni or Co is combined with a reducing agent such as organoaluminum; organometallic compounds or complexes of Ru, Rh, etc.; fullerenes or carbon nanotubes that have absorbed hydrogen, etc. These may be used alone or in combination of two or more.

[0135] Among these, metallocene compounds containing any of Ti, Zr, Hf, Co, and Ni are preferred because they can undergo hydrogenation in a homogeneous system in an inert organic solvent. Metallocene compounds containing any of Ti, Zr, and Hf are also preferred. In particular, hydrogenation catalysts obtained by reacting titanocene compounds with alkyllithium are preferred because they are inexpensive and industrially particularly useful. Specific examples include the hydrogenation catalysts described in JP-A Nos. 1-275605, 5-271326, 5-271325, 5-222115, 11-292924, 2000-37632, 59-133203, 63-5401, 62-218403, 7-90017, JP-B Nos. 43-19960 and 47-40473. These hydrogenation catalysts may be used alone or in combination of two or more.

[0136] (Photosensitive resin composition) Next, the photosensitive resin composition of the present disclosure will be described. The photosensitive resin composition of the present disclosure contains the polymer of the present disclosure. The polymer of the present disclosure may be used alone or in combination of two or more types.

[0137] The content of the polymer of the present disclosure in 100% by mass of the photosensitive resin composition of the present disclosure is preferably 30 to 99% by mass, more preferably 40 to 95% by mass, and even more preferably 50 to 90% by mass. This tends to more suitably obtain the effects of the present disclosure.

[0138] The compounding ingredients that can be contained in the photosensitive resin composition of the present disclosure will be described below.

[0139] <Solvent> The photosensitive resin composition of the present disclosure preferably contains a solvent. In the photosensitive resin composition of the present disclosure, the solvent is not particularly limited as long as it dissolves the polymer of the present disclosure, and examples thereof include ketones, alcohols, polyhydric alcohols and derivatives thereof, ethers, esters, aromatic solvents, and fluorine-based solvents. These may be used alone or in combination of two or more.

[0140] Examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, methyl isobutyl ketone, methyl isopentyl ketone, 2-heptanone, etc. Examples of alcohols include isopropanol, butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, oleyl alcohol, etc.

[0141] Examples of polyhydric alcohols and derivatives thereof include ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA), monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0142] Examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0143] Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, γ-butyrolactone, etc. Examples of aromatic solvents include xylene, toluene, etc.

[0144] Examples of fluorine-based solvents include chlorofluorocarbons, chlorofluorocarbon substitutes, perfluoro compounds, and hexafluoroisopropyl alcohol.

[0145] In addition, for the purpose of improving the coating property, turpentine-based petroleum naphtha solvents and paraffin-based solvents, which are high-boiling weak solvents, can be used.

[0146] Among these, the solvents include methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monoa The solvent is preferably at least one selected from the group consisting of dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol monoacetate monobutyl ether, dipropylene glycol monoacetate monophenyl ether, 1,4-dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, γ-butyrolactone, and hexafluoroisopropyl alcohol. Methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone are more preferred.

[0147] The amount of solvent in the photosensitive resin composition of the present disclosure is preferably in the range of 50 to 2000 parts by mass, more preferably 100 to 1000 parts by mass, per 100 parts by mass of the solid content. By adjusting the amount of solvent, it is possible to adjust the film thickness of the resin film to be formed. In this specification, the solid content refers to the heating residue when the photosensitive resin composition is heated at 130°C for 2 hours, and usually refers to a polymer compound (polymer, resin, polymer) such as the polymer of the present disclosure.

[0148] <Photopolymerization Initiator> The photosensitive resin composition of the present disclosure preferably contains a photopolymerization initiator. This allows the photosensitive resin composition of the present disclosure to be suitably used as a negative-type photosensitive resin composition. In the photosensitive resin composition of the present disclosure, the photopolymerization initiator is not particularly limited as long as it polymerizes a monomer by high-energy radiation such as electromagnetic waves or electron beams, and known photopolymerization initiators can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), and a photoanionic polymerization initiator (photobase generator). These may be used alone, or two or more types of photoradical polymerization initiators, photoacid generators, and photobase generators may be used in combination, or two or more types of photoradical polymerization initiators, photoacid generators, or photobase generators may be mixed and used. Furthermore, by using an additive in combination with the photopolymerization initiator, living polymerization may be performed in some cases, and known additives can be used.

[0149] The photoradical polymerization initiator can be classified into, for example, an intramolecular cleavage type in which an intramolecular bond is cleaved by absorption of an electromagnetic wave or an electron beam to generate a radical, and a hydrogen abstraction type in which a radical is generated by using a hydrogen donor such as a tertiary amine or an ether in combination, and any of these may be used. Photoradical polymerization initiators other than those listed above may also be used.

[0150] Specific examples of the photoradical polymerization initiator include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, acyloin-based, and oxime ester-based initiators.

[0151] Examples of benzophenone-based compounds include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc. Of these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.

[0152] Examples of acetophenone-based compounds include acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. Of these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

[0153] Examples of diketones include 4,4'-dimethoxybenzyl, methyl benzoylformate, 9,10-phenanthrenequinone, etc. Among these, 4,4'-dimethoxybenzyl and methyl benzoylformate are preferred.

[0154] Examples of acylphosphine oxides include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0155] Examples of quinones include anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone, etc. Among these, camphorquinone and 1,4-naphthoquinone are preferred.

[0156] Examples of acyloin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. Of these, benzoin and benzoin methyl ether are preferred.

[0157] Examples of oxime esters include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, and among these, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone is preferred.

[0158] As the photoradical polymerization initiator, acylphosphine oxide-based and oxime ester-based initiators are preferred, and acylphosphine oxide-based initiators are more preferred.

[0159] Among commercially available photoradical polymerization initiators, preferred ones include those manufactured by BASF Inc. under the following product names: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01, Darocur 1173, Lucirin TPO, and Omnirad 819.

[0160] Examples of the photoacid generator include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bisalkyl or bisaryl sulfonyl diazomethanes and poly(bissulfonyl)diazomethanes, nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.

[0161] Specific examples of onium salt acid generators include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, tri(4-methylphenyl)sulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, dimethyl(4-hydroxynaphthyl)sulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, monophenyldimethylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, diphenylmonomethylsulfonium trifluoromethanesulfonate, nitrate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, (4-methylphenyl)diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, tri(4-tert-butyl)phenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, diphenyl(1-(4-methoxy)naphthyl)sulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, di(1-naphthyl)phenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, and the like. Furthermore, onium salts in which the anion moiety of these onium salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.

[0162] Specific examples of oxime sulfonate acid generators include α-(p-toluenesulfonyloxyimino)-benzyl cyanide, α-(p-chlorobenzenesulfonyloxyimino)-benzyl cyanide, α-(4-nitrobenzenesulfonyloxyimino)-benzyl cyanide, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimino)-benzyl cyanide, α-(benzenesulfonyloxyimino)-4-chlorobenzyl cyanide, α-(benzenesulfonyloxyimino)-2,4-dichlorobenzyl cyanide, α-(benzenesulfonyloxyimino)-4-chlorobenzyl cyanide, α-(benzenesulfonyloxyimino)-2,4-dichlorobenzyl cyanide, α-(4-dodecylbenzenesulfonyloxyimino)-benzyl cyanide, α-(benzenesulfonyloxyimino)-2,6-dichlorobenzyl cyanide, α-(benzenesulfonyloxyimino)-4-methoxybenzyl cyanide, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxybenzyl cyanide, α-(benzenesulfonyloxyimino)-thien-2-ylacetonitrile, α-(4-dodecylbenzenesulfonyloxyimino)-benzyl cyanide, α-[(p-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(dodecylbenzenesulfonyloxyimino)- 4-Methoxyphenyl]acetonitrile, α-(tosyloxyimino)-4-thienyl cyanide, α-(methylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-1-cycloheptenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclooctenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-1-cyclopentenylacetonitrile α-(cyclohexylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile,α-(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(n-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(n-butylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methyl Examples thereof include α-(ethylsulfonyloxyimino)-p-methoxyphenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-p-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-p-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-p-methylphenylacetonitrile, and α-(methylsulfonyloxyimino)-p-bromophenylacetonitrile.

[0163] Specific examples of diazomethane acid generators such as bisalkyl or bisarylsulfonyldiazomethanes and poly(bissulfonyl)diazomethanes include bis(isopropylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(2,4-dimethylphenylsulfonyl)diazomethane.

[0164] Examples of the photobase generator include 1-(anthraquinone-2-yl)ethyl N-cyclohexylcarbamate, 9-anthrylmethyl N,N-diethylcarbamate, 9-anthrylmethyl piperidine-1-carboxylate, 9-anthrylmethyl N,N-dicyclohexylcarbamate, 1-(anthraquinone-2-yl)ethyl N,N-dicyclohexylcarbamate, 1-(anthraquinone-2-yl)ethyl imidazole-1-carboxylate, cyclohexylammonium 2-(3-benzoylphenyl)propionate, (E)-N-cyclohexyl-3-(2-hydroxyphenyl)acrylamide, di ... 4-(3-benzoylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propionate, 4-hydroxypiperidine-1-carboxylate (2-nitrophenyl)methyl, 4-(methacryloyloxy)piperidine-1-carboxylate (2-nitrophenyl)methyl, guanidium 2-(3-benzoylphenyl)propionate, and (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propen-1-one.

[0165] Examples of commercially available photobase generators include those manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. under the product names WPBG-300, WPBG-345, WPBG-266, WPBG-018, WPBG-027, WPBG-140, and WPBG-165; those manufactured by BASF Japan Ltd. under the product names CGI-325, Irgacure OXE01, and Irgacure OXE02; and those manufactured by ADEKA Corporation under the product names N-1919 and NCI-831.

[0166] The content of the photopolymerization initiator in the photosensitive resin composition of the present disclosure is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the solid content. When the content of the photopolymerization initiator is 0.1 part by mass or more, a sufficient crosslinking effect tends to be obtained, and when it is 30 parts by mass or less, better resolution and sensitivity tend to be obtained.

[0167] <Crosslinking Agent> The photosensitive resin composition of the present disclosure preferably contains a crosslinking agent, and more preferably contains a crosslinking agent together with a photopolymerization initiator. This tends to more effectively crosslink the polymer and improve the mechanical strength of the film formed. In addition, the photosensitive resin composition of the present disclosure can be suitably used as a negative-type photosensitive resin composition.

[0168] Known crosslinking agents can be used, and specific examples include compounds in which an amino group-containing compound such as melamine, acetoguanamine, benzoguanamine, urea, ethyleneurea, propyleneurea, or glycoluril is reacted with formaldehyde or formaldehyde and a lower alcohol, and the hydrogen atoms of the amino group are substituted with hydroxymethyl groups or lower alkoxymethyl groups, polyfunctional epoxy compounds, polyfunctional oxetane compounds, polyfunctional isocyanate compounds, and polyfunctional acrylate compounds. Here, those using melamine are called melamine-based crosslinking agents, those using urea are called urea-based crosslinking agents, those using alkylene ureas such as ethyleneurea and propyleneurea are called alkylene urea-based crosslinking agents, and those using glycoluril are called glycoluril-based crosslinking agents. These crosslinking agents may be used alone or in combination of two or more.

[0169] The crosslinking agent is preferably at least one selected from these crosslinking agents, and particularly preferably a melamine-based crosslinking agent, a polyfunctional acrylate compound, or a polyfunctional epoxy compound, and more preferably a polyfunctional acrylate compound or a polyfunctional epoxy compound.

[0170] Examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine, with hexamethoxymethylmelamine being particularly preferred.

[0171] Examples of urea-based crosslinking agents include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, and among these, bismethoxymethylurea is preferred.

[0172] Examples of the alkylene urea crosslinking agent include ethylene urea crosslinking agents such as mono- and / or dihydroxymethylated ethylene urea, mono- and / or dimethoxymethylated ethylene urea, mono- and / or diethoxymethylated ethylene urea, mono- and / or dipropoxymethylated ethylene urea, and mono- and / or dibutoxymethylated ethylene urea; propylene urea crosslinking agents such as mono- and / or dihydroxymethylated propylene urea, mono- and / or dimethoxymethylated propylene urea, mono- and / or diethoxymethylated propylene urea, mono- and / or dipropoxymethylated propylene urea, and mono- and / or dibutoxymethylated propylene urea; 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0173] Examples of glycoluril crosslinking agents include mono-, di-, tri-, and / or tetrahydroxymethylated glycoluril, mono-, di-, tri-, and / or tetramethoxymethylated glycoluril, mono-, di-, tri-, and / or tetraethoxymethylated glycoluril, mono-, di-, tri-, and / or tetrapropoxymethylated glycoluril, and mono-, di-, tri-, and / or tetrabutoxymethylated glycoluril.

[0174] Examples of polyfunctional acrylate compounds include polyfunctional acrylates (e.g., product names A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol diacrylates (e.g., product names A-200, A-400, A-600, manufactured by Shin-Nakamura Chemical Co., Ltd.), urethane acrylates (e.g., product names UA-122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, UA-7200, manufactured by Shin-Nakamura Chemical Co., Ltd.), pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

[0175] Preferred examples of the polyfunctional acrylate compound are shown below.

[0176]

[0177]

[0178]

[0179]

[0180] Examples of polyfunctional epoxy compounds include sorbitol polyglycidyl ethers (for example, trade names "Denacol EX-614" and "Denacol EX-614B" manufactured by Nagase ChemteX Corporation), polyglycerol polyglycidyl ethers (for example, trade names "Denacol EX-512" and "Denacol EX-521" manufactured by Nagase ChemteX Corporation), pentaerythritol polyglycidyl ethers, diglycerol polyglycidyl ethers (for example, trade names "Denacol EX-421" manufactured by Nagase ChemteX Corporation, and trade name "SR-4GL" manufactured by Sakamoto Pharmaceutical Co., Ltd.), glycerol polyglycidyl ethers (for example, trade names "Denacol EX-313" and "Denacol EX-314" manufactured by Nagase ChemteX Corporation, and trade name " SR-GLG" and the like), (poly)ethylene glycol diglycidyl ethers (for example, trade names "DENACOL EX-810", "DENACOL EX-811", "DENACOL EX-850", "DENACOL EX-851", "DENACOL EX-821", "DENACOL EX-830", "DENACOL EX-832", "DENACOL EX-841", and "DENACOL EX-861" manufactured by Nagase ChemteX Corporation, and trade names "SR-EGM", "SR-8EG", and "SR-8EGS" manufactured by Sakamoto Pharmaceutical Co., Ltd.), (poly)propylene glycol diglycidyl ethers (for example, trade names "DENACOL EX-911", "DENACOL EX-941", and "DENACOL EX-920" manufactured by Nagase ChemteX Corporation, and trade name "SR-PG" manufactured by Sakamoto Pharmaceutical Co., Ltd.), and the like.

[0181] The content of the crosslinking agent in the photosensitive resin composition of the present disclosure is preferably 3 to 400 parts by mass, and more preferably 5 to 300 parts by mass, per 100 parts by mass of the solid content. When the content of the crosslinking agent is 3 parts by mass or more, a sufficient crosslinking effect tends to be obtained, and when it is 400 parts by mass or less, better resolution and sensitivity tend to be obtained.

[0182] <Alkali-Soluble Resin> The photosensitive resin composition of the present disclosure may contain an alkali-soluble resin. The alkali-soluble resin may be used alone or in combination of two or more kinds.

[0183] The alkali-soluble resin is not particularly limited as long as it is a resin that is soluble in alkali, and examples thereof include alkali-soluble novolak resins, which can be obtained by condensing phenols and aldehydes in the presence of an acid catalyst.

[0184] Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methyl-catechol, pyrogallol, phloroglucinol, thymol, isothymol, etc. These phenols may be used alone or in combination of two or more.

[0185] Examples of aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde. Examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, and p-toluenesulfonic acid. These acid catalysts may be used alone or in combination of two or more.

[0186] Other examples of alkali-soluble resins include epoxy (meth)acrylate acid adducts (acid-modified epoxy (meth)acrylate alkali-soluble resins) obtained by reacting an epoxy compound (bisphenol-type epoxy compound) having two glycidyl ether groups derived from a bisphenol with (meth)acrylic acid, and then reacting the resulting compound having a hydroxy group with a polybasic carboxylic acid or its anhydride. Commercially available acid-modified epoxy acrylates include those manufactured by Nippon Kayaku Co., Ltd. under the product names: CCR-1218H, CCR-1159H, CCR-1222H, CCR-1291H, CCR-1235, PCR-1050, TCR-1335H, UXE-3024, ZAR-1035, ZAR-2001H, ZFR-1185, ZCR-1569H, and ZAR-2050H.

[0187] The epoxy compound having two glycidyl ether groups derived from a bisphenol refers to an epoxy compound having two glycidyl ether groups obtained by reacting a bisphenol with an epihalohydrin, or an equivalent thereof. This reaction generally involves oligomerization of the diglycidyl ether compound, and therefore includes epoxy compounds having two or more bisphenol skeletons.

[0188] Examples of bisphenols include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane , 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy- 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, and the like.These may be used alone or in combination of two or more.

[0189] Examples of polybasic carboxylic acids or anhydrides thereof include monoanhydrides of dicarboxylic acids or tricarboxylic acids, dianhydrides of tetracarboxylic acids, etc. These may be used alone or in combination of two or more.

[0190] Examples of dicarboxylic or tricarboxylic acid monoanhydrides include acid monoanhydrides of chain hydrocarbon dicarboxylic or tricarboxylic acids, acid monoanhydrides of alicyclic dicarboxylic or tricarboxylic acids, and acid monoanhydrides of aromatic dicarboxylic or tricarboxylic acids. These may be used alone or in combination of two or more. Examples of acid monoanhydrides of chain hydrocarbon dicarboxylic or tricarboxylic acids include acid monoanhydrides of succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid. Examples of acid monoanhydrides of alicyclic dicarboxylic or tricarboxylic acids include acid monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid. Examples of the acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, and the like.

[0191] Examples of tetracarboxylic acid dianhydrides include acid dianhydrides of chain hydrocarbon tetracarboxylic acids, acid dianhydrides of alicyclic tetracarboxylic acids, and acid dianhydrides of aromatic tetracarboxylic acids. These may be used alone or in combination of two or more. Examples of acid dianhydrides of chain hydrocarbon tetracarboxylic acids include acid dianhydrides such as butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid. Examples of acid dianhydrides of alicyclic tetracarboxylic acids include acid dianhydrides such as cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid. Examples of acid dianhydrides of aromatic tetracarboxylic acids include acid dianhydrides such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and biphenyl ether tetracarboxylic acid.

[0192] The weight average molecular weight of the alkali-soluble resin component is preferably from 1,000 to 50,000 from the viewpoint of the developability and resolution of the photosensitive resin composition.

[0193] The content of the alkali-soluble resin in the photosensitive resin composition of the present disclosure is preferably 10 to 200 parts by mass, and more preferably 20 to 100 parts by mass, relative to 100 parts by mass of the polymer of the present disclosure.

[0194] <Naphthoquinone diazide group-containing compound> The photosensitive resin composition of the present disclosure preferably contains a naphthoquinone diazide group-containing compound. This allows the photosensitive resin composition of the present disclosure to be suitably used as a positive-type photosensitive resin composition. When the photosensitive resin composition of the present disclosure contains a naphthoquinone diazide group-containing compound, the shape of the cured product obtained from the photosensitive resin composition of the present disclosure tends to be more favorable. The naphthoquinone diazide group-containing compound is not particularly limited, and any compound typically used as a photosensitive component in i-line resist compositions can be used.

[0195] Specific examples of naphthoquinone diazide group-containing compounds include naphthoquinone-1,2-diazide-4-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-5-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-6-sulfonic acid ester compounds, naphthoquinone-1,2-diazide sulfonic acid ester compounds, orthobenzoquinone diazide sulfonic acid ester compounds, and orthoanthraquinone diazide sulfonic acid ester compounds. Among these, naphthoquinone-1,2-diazide-4-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-5-sulfonic acid ester compounds, and naphthoquinone-1,2-diazide-6-sulfonic acid ester compounds are preferred due to their excellent solubility. These compounds may be used alone or in combination of two or more.

[0196] The content of the naphthoquinone diazide group-containing compound in the photosensitive resin composition of the present disclosure is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the solid content. When the content is 60 parts by mass or less, the photosensitive resin composition tends to have better sensitivity.

[0197] <Basic Compound> The photosensitive resin composition of the present disclosure may contain a basic compound. The basic compound has the function of slowing down the diffusion rate of the acid generated from the photoacid generator when it diffuses into the film of the photosensitive resin composition of the present disclosure. By incorporating a basic compound, it is possible to adjust the acid diffusion distance, and it tends to be possible to improve the shape of the cured product. Furthermore, by incorporating a basic compound, it tends to be possible to make the film less likely to deform even if the exposure time after film formation is long, and it tends to be possible to stably form a cured product with the desired precision.

[0198] Examples of basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, and aliphatic polycyclic amines. Among these, aliphatic amines are preferred, and specific examples include secondary or tertiary aliphatic amines, alkyl alcohol amines, and the like. These may be used alone or in combination of two or more.

[0199] Examples of aliphatic amines include ammonia (NH ３ ) in which at least one hydrogen atom has been substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms. Specific examples thereof include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, and di-n-octylamine. , di-n-nonylamine, di-n-decanylamine, di-n-dodecylamine, dicyclohexylamine, methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decanylamine, n-dodecylamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, etc. Among these, dialkylamines, trialkylamines, and alkyl alcoholamines are preferred, and alkyl alcoholamines are more preferred. Of the alkyl alcoholamines, triethanolamine and triisopropanolamine are particularly preferred.

[0200] Examples of aromatic amines and heterocyclic amines include aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine; heterocyclic amines such as 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, pyridine, bipyridine, 4-dimethylaminopyridine, hexamethylenetetramine, and 4,4-dimethylimidazoline; 6-pentamethyl-4-piperidyl) sebagate and other hindered amines; 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine and other alcoholic nitrogen-containing compounds; picoline, lutidine, pyrrole, piperidine, piperazine, indole, hexamethylenetetramine and other.

[0201] In the photosensitive resin composition of the present disclosure, the content of the basic compound is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of the solid content. When the amount of the basic compound is 0.001 part by mass or more, the effect as an additive is sufficiently obtained, and when it is 2 parts by mass or less, better resolution and sensitivity tend to be obtained.

[0202] <Weak Acid Photoacid Generator (Weak Acid PAG)> The photosensitive resin composition of the present disclosure may contain a weak acid photoacid generator (weak acid PAG). The weak acid PAG exhibits the same action and effect as the above-mentioned basic compound. Therefore, in this specification, the weak acid PAG is a component different from the above-mentioned photopolymerization initiator (photoacid generator). When a component also corresponds to the above-mentioned photopolymerization initiator (photoacid generator), it is treated as a weak acid PAG rather than the above-mentioned photopolymerization initiator (photoacid generator).

[0203] The weak acid PAG may also be a photodegradable base that is photosensitive upon exposure to generate a weak acid. Examples of the photodegradable base include onium salt compounds that decompose upon exposure to light. Examples of the onium salt compound include sulfonium salt compounds represented by the following formula (9-1) and iodonium salt compounds represented by the following formula (9-2).

[0204] (In the above formula (9-1) and formula (9-2), R ５ ~R ９ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom. － and Q － are each independently OH － , R β -COO － , R β -SO ３ － Or an anion represented by the following formula (9-3): β is an alkyl group, an aryl group, or an aralkyl group.

[0205] (In the above formula (9-3), R １０ represents a linear or branched alkyl group having 1 to 12 carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms, or a linear or branched alkoxy group having 1 to 12 carbon atoms; and u represents an integer of 0 to 2.

[0206] Specific examples of weak acid PAGs include the following compounds:

[0207]

[0208] <Other Additives> The photosensitive resin composition of the present disclosure may contain other additives as needed. Examples of other additives include fillers, dissolution inhibitors, plasticizers, stabilizers, colorants, surfactants, thickeners, leveling agents, antifoaming agents, compatibilizers, adhesion agents, antioxidants, and chain transfer agents. These may be used alone or in combination of two or more. These other additives may be known.

[0209] As the surfactant, it is preferable to contain, for example, one or more of a fluorine-based or silicon-based surfactant (a fluorine-based surfactant and a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom).

[0210] The incorporation of an adhesive agent tends to exhibit better adhesion to the substrate. Examples of adhesive agents include silane coupling agents and phosphate esters. Examples of silane coupling agents include sulfide-based, mercapto-based, protected mercapto-based, vinyl-based, amino-based, glycidoxy-based, nitro-based, and chloro-based agents. These may be used alone or in combination of two or more. Of these, vinyl-based agents are preferred, and (meth)acrylic phosphorus-containing compounds are more preferred. Examples of (meth)acrylic phosphorus-containing compounds include KBM-503 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd. As phosphate esters, those having vinyl, acrylic, or methacrylic groups at the crosslinking site are desirable, such as KAYAMER-PM21 manufactured by Nippon Kayaku Co., Ltd.

[0211] In the photosensitive resin composition of the present disclosure, the content of the adhesive agent is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the solid content, which tends to exhibit better adhesion to the substrate.

[0212] Examples of colorants include color pigments, color dyes, etc. These may be used alone or in combination of two or more.

[0213] Examples of color pigments include color inorganic pigments such as titanium dioxide, carbon black, graphite, iron oxide, and coal dust; color organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone, perylene, anthrapyrimidine, carbazole violet, anthrapyridine, azo orange, flavanthrone yellow, isoindoline yellow, azo yellow, industhrone blue, dibromoanzathrone red, perylene red, azo red, and anthraquinone red; and aluminum powder, alumina powder, bronze powder, copper powder, tin powder, zinc powder, iron phosphide, and finely divided titanium.

[0214] Examples of organic pigments that can be used include, but are not limited to, those with the following color index numbers: Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment Green 7, 36, 58, etc. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc. Pigment Violet 19, 23, 37, etc.

[0215] Examples of coloring dyes include monoazo dyes, disazo dyes, metal complex monoazo dyes, anthraquinone dyes, methine dyes, phthalocyanine dyes, and triarylmethane dyes.

[0216] Colorants are typically dispersed in a solvent and mixed with other ingredients as a colorant dispersion, and a dispersant may be added in this case. The dispersant may be any known compound used in pigment (colorant) dispersion (e.g., compounds commercially available under the names dispersant, dispersing wetting agent, dispersion promoter, etc.), and the like, without any particular restrictions. Examples of dispersants include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersion aids). These may be used alone or in combination of two or more. The amount of dispersant added is preferably 1 to 35% by mass, and more preferably 2 to 25% by mass, of the colorant. High-viscosity substances such as resins generally have the effect of stabilizing dispersion, but those without dispersion-promoting properties are not considered dispersants. However, this does not limit their use for the purpose of stabilizing dispersion.

[0217] In the photosensitive resin composition of the present disclosure, the content of the colorant is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the solid content.

[0218] A chain transfer agent is a component that receives a radical from a growing polymer chain in a radical polymerization system and generates a new radical. By using a chain transfer agent, the degree of polymerization can be adjusted, and the properties of the cured product can be adjusted. Examples of chain transfer agents include aromatic hydrocarbons; halogenated hydrocarbons such as chloroform, carbon tetrachloride, carbon tetrabromide, and bromotrichloromethane; mercaptan compounds such as octyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, n-dodecyl mercaptan, t-tetradecyl mercaptan, and t-dodecyl mercaptan; hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, Ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, pentaerythritol Examples of suitable thiol compounds include tetrakis(3-mercaptobutyrate); sulfide compounds such as dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide; N,N-dimethylaniline, N,N-divinylaniline, pentaphenylethane, α-methylstyrene dimer, acrolein, allyl alcohol, terpinolene, α-terpinene, γ-terpinene, and dipentene. These may be used alone or in combination of two or more. Of these, thiol compounds are preferred.

[0219] In the photosensitive resin composition of the present disclosure, the content of the chain transfer agent is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the solid content, which makes it possible to maintain appropriate curability and adjust the development contrast with the unexposed area.

[0220] (Method for producing a cured product, and method for producing a substrate with a patterned film) Next, a method for producing a cured product using the photosensitive resin composition of the present disclosure and a method for producing a substrate with a patterned film will be described.

[0221] The method for producing a cured product (a method for producing a substrate with a patterned film) according to the present disclosure is not particularly limited as long as it can cure the photosensitive resin composition according to the present disclosure, and may include, for example, (1-1) a film-forming step, (1-2) an exposure step, and (1-3) a development step, and may further include (1-4) a baking step. Each step is described below.

[0222] (1-1) Film Forming Step First, in the film forming step, the photosensitive resin composition of the present disclosure is applied to a substrate to form a film. Specifically, after the photosensitive resin composition of the present disclosure is applied to a substrate, the composition is heated to remove the solvent, and the photosensitive resin composition is turned into a film. The heating conditions are not particularly limited, but are preferably 80 to 100°C and 60 to 200 seconds. This allows the solvent and other components contained in the photosensitive resin composition to be removed.

[0223] The substrate may be a silicon wafer, metal, glass, ITO substrate, or the like. An organic or inorganic film may be pre-formed on the substrate. For example, an anti-reflective film, a lower layer of a multilayer resist, metal wiring, an interlayer insulating film, or a stress relaxation layer may be present, and a pattern may be formed thereon. The substrate may also be formed with imaging elements such as CCDs and CMOS, light-emitting elements such as LEDs, control elements such as transistors and capacitors, and connection paths such as vias. The substrate may also be pre-washed. For example, it can be washed using ultrapure water, acetone, alcohol (methanol, ethanol, isopropyl alcohol), or the like.

[0224] The photosensitive resin composition of the present disclosure can be applied to a substrate using an appropriate coating device such as a slit coater, a die coater, a gravure coater, a dip coater, a spin coater, etc. Alternatively, methods such as dip coating, spray coating, and roller coating can also be used.

[0225] Here, the film formed on the substrate may be formed on the entire surface of the substrate, or may be formed on only a part of the substrate.

[0226] The thickness of the film is preferably 0.1 to 500 μm. If the film is thinner than 0.1 μm, the mechanical strength of the film may decrease, and if the film is thicker than 500 μm, the surface irregularities tend to increase, making it difficult to obtain a flat film.

[0227] (1-2) Exposure Step Next, in the exposure step, the film after the film-forming step is exposed to high-energy rays through a photomask for forming a desired pattern, and the pattern of the photomask is transferred to the film. Specifically, a desired photomask is set in an exposure device, and the film after the film-forming step is exposed to high-energy rays through the photomask. Alternatively, exposure can be performed using a high-energy ray direct writing device. The high-energy rays are preferably at least one type selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and alpha rays. Heating may be performed as necessary to promote curing. The heating conditions are not particularly limited, but are preferably 80 to 150°C and 60 to 300 seconds.

[0228] The exposure dose of high energy rays is 1 to 2000 mJ / cm ２ is preferably 10 to 1000 mJ / cm ２ It is more preferable that:

[0229] (1-3) Development Step Next, in the development step, the film after the exposure step is developed with a developer to obtain a patterned film. Specifically, the film after the exposure step is developed with an alkaline aqueous solution and / or an organic solvent to obtain a patterned film. That is, either the exposed portion of the film or the unexposed portion of the film is dissolved in an alkaline aqueous solution and / or an organic solvent to obtain a patterned film.

[0230] Examples of aqueous alkaline solutions that can be used include aqueous tetramethylammonium hydroxide (TMAH) solutions, aqueous tetrabutylammonium hydroxide (TBAH) solutions, aqueous potassium hydroxide solutions, and aqueous sodium carbonate solutions. These may be used alone or in combination of two or more. When the aqueous alkaline solution is an aqueous tetramethylammonium hydroxide (TMAH) solution, its concentration is preferably 0.1 to 5% by mass, and more preferably 2 to 3% by mass.

[0231] Examples of organic solvents include butyl acetate, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, and ethyl crotonate. methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, etc. These may be used alone or in combination of two or more.

[0232] As the developing method, a known method can be used, for example, a dipping method, a puddle method, a spray method, or the like.

[0233] The development time (the time during which the developer is in contact with the film) is preferably from 10 seconds to 10 minutes, and more preferably from 30 seconds to 5 minutes.

[0234] After development, a step of washing the pattern film with deionized water, etc. may be performed as needed. The washing method and washing time are preferably 10 seconds to 3 minutes, and more preferably 30 seconds to 2 minutes.

[0235] (1-4) Baking Step In the baking step, after the developing step, the patterned film is baked to cure it, thereby obtaining a cured product. Specifically, after the developing step, the patterned film is heated and baked to cure it, thereby obtaining a cured product. The cured product of the present disclosure is obtained by curing the photosensitive resin composition of the present disclosure. Baking can be performed on a hot plate, and the baking conditions are preferably 60 to 300°C and 10 to 120 minutes.

[0236] Through the above steps, a pattern can be formed.

[0237] The photosensitive resin composition of the present disclosure can be used not only to form films that exist for a predetermined period of time and are removed when no longer needed, like photoresists, but also to form permanent films (cured products) that remain in products without being removed after formation.

[0238] (Applications) The cured product of the present disclosure obtained by curing the photosensitive resin composition of the present disclosure has good thermal stability and excellent adhesiveness (adhesion), and therefore can be suitably used as an adhesive layer. In addition, the cured product of the present disclosure has good thermal stability and excellent performance (for example, a uniform cured product with no individual differences and good yield and performance), and therefore can be suitably used not only as an adhesive layer, but also as, for example, a protective film, an insulating film (preferably an interlayer insulating film (for example, an interlayer insulating film for a display, an interlayer insulating film covering a rewiring layer of a semiconductor device)), or a planarizing film (for example, a planarizing film covering a transistor). In addition, the cured product of the present disclosure has good thermal stability and excellent transparency with no scattering, etc., and therefore can be suitably used as an optical filter.

[0239] The cured product of the present disclosure can also be suitably used as a simple film without a pattern.

[0240] (Adhesive) The cured product of the present disclosure has good thermal stability and excellent adhesiveness (adhesion), and therefore can be suitably used as an adhesive layer. Therefore, the photosensitive resin composition of the present disclosure can be suitably used as an adhesive. It is presumed that the good adhesiveness (adhesion) of the cured product of the present disclosure is due to the lipophilicity of the polymer. Therefore, the adhesive of the present disclosure is composed of the photosensitive resin composition of the present disclosure. The photosensitive resin composition of the present disclosure may be used alone or in combination of two or more types.

[0241] The content of the photosensitive resin composition of the present disclosure in 100% by mass of the adhesive of the present disclosure is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 100% by mass, which tends to more suitably obtain the effects of the present disclosure.

[0242] (Electronic Device) The electronic device of the present disclosure is not particularly limited as long as it is an electronic device including the cured product of the present disclosure. An example of an electronic device including the cured product of the present disclosure will be described below. FIG. 1 is a cross-sectional view showing an example of an electronic device 100 according to the present embodiment. The electronic device 100 according to the present embodiment includes an insulating film 20, which is a permanent film formed, for example, from the photosensitive resin composition of the present disclosure.

[0243] 1 shows a liquid crystal display device as an example of the electronic device 100 according to the present embodiment. However, the electronic device 100 according to the present embodiment is not limited to a liquid crystal display device, and includes other electronic devices that include a permanent film made of the cured product of the present disclosure.

[0244] As shown in FIG. 1, an electronic device 100, which is a liquid crystal display device, includes, for example, a substrate 10, a transistor 30 provided on the substrate 10, an insulating film 20 provided on the substrate 10 so as to cover the transistor 30, and wiring 40 provided on the insulating film 20.

[0245] The substrate 10 is, for example, a glass substrate. The transistor 30 is, for example, a thin-film transistor constituting a switching element of a liquid crystal display device. For example, a plurality of transistors 30 are arranged in an array on the substrate 10. The transistor 30 according to this embodiment is composed of, for example, a gate electrode 31, a source electrode 32, a drain electrode 33, a gate insulating film 34, and a semiconductor layer 35. The gate electrode 31 is provided on, for example, the substrate 10. The gate insulating film 34 is provided on the substrate 10 so as to cover the gate electrode 31. The semiconductor layer 35 is provided on the gate insulating film 34. The semiconductor layer 35 is, for example, a silicon layer. The source electrode 32 is provided on the substrate 10 so as to be in partial contact with the semiconductor layer 35. The drain electrode 33 is provided on the substrate 10 so as to be spaced apart from the source electrode 32 and so as to be in partial contact with the semiconductor layer 35.

[0246] The insulating film 20 functions as a planarizing film for eliminating steps caused by the transistors 30 and the like and for forming a flat surface on the substrate 10. The insulating film 20 is made of a cured product of the photosensitive resin composition of the present disclosure. The insulating film 20 has an opening 22 that penetrates the insulating film 20 so as to connect to the drain electrode 33. Wiring 40 that connects to the drain electrode 33 is formed on the insulating film 20 and within the opening 22. The wiring 40 functions as a pixel electrode that constitutes a pixel together with the liquid crystal. An alignment film 90 is provided on the insulating film 20 so as to cover the wiring 40.

[0247] An opposing substrate 12 is disposed above one surface of the substrate 10 on which the transistors 30 are provided, so as to face the substrate 10. Wiring 42 is provided on one surface of the opposing substrate 12 facing the substrate 10. The wiring 42 is provided at a position facing the wiring 40. An alignment film 92 is provided on the one surface of the opposing substrate 12 so as to cover the wiring 42. Liquid crystal that constitutes a liquid crystal layer 14 is filled between the substrate 10 and the opposing substrate 12.

[0248] The electronic device 100 shown in FIG. 1 is formed, for example, as follows. First, a transistor 30 is formed on a substrate 10. Next, a photosensitive resin composition according to the present disclosure is applied by printing or spin coating to the surface of the substrate 10 on which the transistor 30 is provided, thereby forming an insulating film 20 covering the transistor 30. This forms a planarization film covering the transistor 30 on the substrate 10. Next, the insulating film 20 is exposed to light and developed to form an opening 22 in a portion of the insulating film 20. At this time, the unexposed portion dissolves in the developer, while the exposed portion remains. This also applies to each example of the electronic device 100 described below. Next, the insulating film 20 is heat-cured. Then, a wiring 40 connected to the drain electrode 33 is formed in the opening 22 of the insulating film 20. Thereafter, a counter substrate 12 is placed on the insulating film 20, and liquid crystal is filled between the counter substrate 12 and the insulating film 20 to form a liquid crystal layer 14. This completes the formation of the electronic device 100 shown in FIG. 1.

[0249] 1, the insulating film 20 is made of a cured product of the photosensitive resin composition of the present disclosure, but other components (e.g., the gate insulating film 34) may also be made of a cured product of the photosensitive resin composition of the present disclosure. In this case, the insulating film 20 may also be made of a cured product other than the photosensitive resin composition of the present disclosure.

[0250] As an example of an electronic device according to this embodiment, FIG. 2 shows a semiconductor device in which a rewiring layer 80 is formed of a permanent film made of the cured product of the present disclosure. FIG. 2 is a cross-sectional view showing an example of an electronic device 130 according to this embodiment. The electronic device 130 shown in FIG. 2 includes a semiconductor substrate on which semiconductor elements such as transistors are provided, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. The uppermost layer of the multilayer wiring layer includes an insulating film 50, which is an interlayer insulating film, and a top-layer wiring 72 provided on the insulating film 50. The top-layer wiring 72 is made of, for example, Al.

[0251] A rewiring layer 80 is provided on the insulating film 50. The rewiring layer 80 includes an insulating film 52 provided on the insulating film 50 so as to cover the top-layer wiring 72, a rewiring 70 provided on the insulating film 52, and an insulating film 54 provided on the insulating film 52 and the rewiring 70. An opening 24 connected to the top-layer wiring 72 is formed in the insulating film 52. The rewiring 70 is formed on the insulating film 52 and in the opening 24 and connected to the top-layer wiring 72. The insulating film 54 is provided with an opening 26 connected to the rewiring 70. The insulating films 52 and 54 are permanent films made of the cured product of the present disclosure. The insulating film 52 can be obtained, for example, by exposing and developing a photosensitive resin composition of the present disclosure applied to the insulating film 50 to form an opening 24, and then heat-curing the composition. The insulating film 54 can be obtained, for example, by exposing and developing a photosensitive resin composition of the present disclosure applied to the insulating film 52 to form an opening 26, and then heat-curing the composition.

[0252] For example, bumps 74 are formed in the openings 26. The electronic device 130 is connected to a wiring board or the like via the bumps 74, for example.

[0253] In the electronic device 130 shown in FIG. 2 , the redistribution layer 80 (insulating film 52, insulating film 54) is composed of a cured product of the photosensitive resin composition of the present disclosure, but other components (e.g., insulating film 50) may be composed of a cured product of the photosensitive resin composition of the present disclosure. In this case, the redistribution layer 80 (insulating film 52, insulating film 54) may be composed of a cured product other than the photosensitive resin composition of the present disclosure. Furthermore, only one of the insulating films 52 and 54 constituting the redistribution layer 80 may be composed of a cured product of the photosensitive resin composition of the present disclosure.

[0254] FIG. 3 is a cross-sectional view showing an example of an electronic device (semiconductor device) 210 according to this embodiment. The semiconductor device 210 shown in FIG. 3 is an example having a BGA (Ball Grid Array) type semiconductor package. The semiconductor device 210 includes a plurality of stacked semiconductor chips 220 (semiconductor elements), an adhesive layer 601 that bonds the semiconductor chips 220 together, a package substrate 230 that supports the semiconductor chips 220, an adhesive layer 201 that bonds the semiconductor chips 220 to the package substrate 230, a molded portion 250 that seals the semiconductor chips 220, and solder balls 280 provided below the package substrate 230. The configuration of each portion will be described in detail below.

[0255] The semiconductor chip 220 may be any type of element, such as a memory element such as a NAND (Not AND) flash memory or a DRAM (Dynamic Random Access Memory), or an integrated circuit element such as an IC (Integrated Circuit) or an LSI (Large Scale Integration).

[0256] The constituent material of the semiconductor chip 220 is not particularly limited, but examples thereof include single crystal materials such as silicon, silicon carbide, and compound semiconductors, polycrystalline materials, and amorphous materials.

[0257] The multiple semiconductor chips 220 are stacked with slight offsets from one another in the in-plane direction, thereby constituting a chip stack 200 (stacked semiconductor element). The semiconductor chips 220 are bonded to one another via an adhesive layer 601. The adhesive layer 601 is also provided on the top surface of the chip stack 200. The adhesive layer 601 is also made of the cured product of the present disclosure. Thus, the semiconductor device 210 includes a chip stack 200 (stacked semiconductor element), and the chip stack 200 (stacked semiconductor element) has multiple semiconductor chips 220 (semiconductor elements) and adhesive layers 601 that are provided between the semiconductor chips 220 (semiconductor elements) and are made of the cured product of the present disclosure, which bonds (adhere) them.

[0258] The package substrate 230 shown in FIG. 3 is a build-up substrate including a core substrate 231 , an insulating layer 232 , a solder resist layer 233 , wiring 234 , and conductive vias 235 .

[0259] The core substrate 231 is a substrate that supports the package substrate 230, and is made of a composite material, for example, glass cloth filled with a resin material.

[0260] The insulating layer 232 is an interlayer insulating layer that insulates the wiring 234 from one another and from the wiring 234 and the conductive vias 235, and is made of, for example, a resin material. The solder resist layer 233 is a surface protection layer that protects the wiring formed on the outermost surface of the package substrate 230, and is made of, for example, a resin material.

[0261] The wiring 234 and the conductive via 235 are each a transmission path for an electrical signal, and are made of a metal material such as a simple substance or alloy of Au, Ag, Cu, Al, or Ni.

[0262] The solder balls 280 are electrically connected to the wiring 234, and when fused to an external electric circuit, function as electrodes for connecting the wiring 234 to other electric circuits.

[0263] Chip stack 200, which is formed by stacking a plurality of semiconductor chips 220, is placed on the upper surface of package substrate 230. Chip stack 200 and package substrate 230 are bonded together by adhesive layer 201.

[0264] Furthermore, a part of the wiring 234 of the package substrate 230 is exposed on the upper surface of the package substrate 230, forming an exposed portion. This exposed portion and the electrode portion of each semiconductor chip 220 are connected by bonding wires 270.

[0265] 3 is configured to cover the side and top surfaces of chip stack 200 and also the entire top surface of package substrate 230. This makes it possible to protect chip stack 200 from the external environment. Such molded portion 250 is made of various resin materials, such as epoxy resin, phenolic resin, or the like.

[0266] The semiconductor device 210 can be manufactured by a manufacturing method including the following steps: a coating step of applying a photosensitive resin composition to a wafer (semiconductor substrate) to form a coating film; an exposure step of exposing the resulting coating film to light; a development step of developing the coating film to pattern it; a processing step of etching and ashing the wafer with the coating film formed thereon; a back-grinding step of grinding the back surface of the wafer; a dicing step of dicing the wafer to separate it into multiple semiconductor chips; and a mounting step of picking up a semiconductor chip and mounting it on a package substrate, and then picking up another semiconductor chip and pressure-bonding it onto the previously mounted semiconductor chip (bonding member). Details of each step are as described in Japanese Patent No. 6702194.

[0267] 3, the adhesive layer 601 is made of a cured product of the photosensitive resin composition of the present disclosure, but other components (e.g., the sealing mold part 250) may also be made of a cured product of the photosensitive resin composition of the present disclosure. In this case, the adhesive layer 601 may also be made of a cured product other than the photosensitive resin composition of the present disclosure. Furthermore, only one of the multiple adhesive layers 601 may also be made of a cured product of the photosensitive resin composition of the present disclosure.

[0268] <Optical Filter> The optical filter of the present disclosure includes the cured product of the present disclosure. The optical filter is used, for example, as a color filter, a black matrix, a light-shielding filter, an anti-reflection filter, an infrared cut filter, an infrared transmission filter, a microlens, etc. The optical filter of the present disclosure can be suitably used in electronic devices.

[0269] <Solid-state imaging element> The solid-state imaging element of the present disclosure has the optical filter of the present disclosure. The solid-state imaging element is not particularly limited as long as it has the optical filter of the present disclosure and functions as a solid-state imaging element, but examples thereof include the following configurations.

[0270] The present invention is configured to include a substrate having a plurality of photodiodes constituting a light-receiving area of ​​a solid-state imaging element (e.g., a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like; a light-shielding film formed on the photodiodes and transfer electrodes, with only the light-receiving portions of the photodiodes exposed; a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes; and an optical filter (color filter) of the present disclosure on the device protective film. Furthermore, the present invention may include a light-focusing means (e.g., a microlens, etc.; the same applies hereinafter) on the device protective film below the optical filter (closer to the substrate), or a light-focusing means on the optical filter. The filter may also have a structure in which a cured film forming each color pixel is embedded in spaces partitioned, for example, in a grid pattern, by partition walls. In this case, the partition walls preferably have a low refractive index relative to the color pixels. An imaging device including the presently disclosed solid-state imaging element can be suitably used in various electronic devices, such as digital cameras, electronic devices with imaging functions (e.g., mobile phones, smartphones, etc.), in-vehicle cameras, and surveillance cameras.

[0271] Hereinafter, an example of an image display device of the present disclosure and an example of an infrared sensor of the present disclosure will be described as examples of electronic devices of the present disclosure that include the optical filter of the present disclosure.

[0272] <Image Display Device> The image display device of the present disclosure is not particularly limited as long as it includes the cured product of the present disclosure. In one preferred embodiment, the image display device of the present disclosure includes the optical filter of the present disclosure. Another preferred embodiment of the image display device of the present disclosure includes an insulating film formed from the cured product of the present disclosure, such as electronic device 100, which is a liquid crystal display device, shown in FIG. 1 . Examples of image display devices include liquid crystal displays (liquid crystal display devices), organic EL displays, micro LED displays, quantum dot displays, and flat panel displays. The configuration used for the image display device is not particularly limited as long as it functions as an image display device. Examples of such configurations include those described in "Next Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994). Definitions of image display devices and details of each image display device are described in, for example, "Electronic Display Devices" (by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (by Nobuaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989).

[0273] <Infrared Sensor> The infrared sensor of the present disclosure includes the optical filter of the present disclosure. The form used for the infrared sensor is not particularly limited as long as it includes the optical filter of the present disclosure and functions as an infrared sensor, but examples include the following configurations.

[0274] A substrate has a plurality of photodiodes constituting the light receiving area of ​​a solid-state imaging device (such as a CCD image sensor or a CMOS image sensor) and transfer electrodes made of polysilicon or the like. A light-shielding film, which is open only to the light receiving portions of the photodiodes, is disposed on the photodiodes and transfer electrodes. A device protective film is disposed on the light-shielding film, and the optical filter of the present disclosure is disposed on the device protective film. Furthermore, the device may have a light-collecting means (e.g., a microlens, etc.; the same applies below) on the device protective film and below the optical filter (on the side closer to the substrate), or may have a light-collecting means on the optical filter.

[0275] Fig. 4 is a cross-sectional view showing an example of an electronic device according to the present disclosure. Specifically, Fig. 4 is a cross-sectional view showing an example of an infrared sensor including an optical filter according to the present disclosure. The infrared sensor 120 shown in Fig. 4 includes a solid-state imaging element 110.

[0276] The imaging area provided on the solid-state imaging device 110 is configured by combining an infrared cut filter 111 and a color filter 112 .

[0277] The infrared cut filter 111 is formed from the cured product of the present disclosure, and transmits light in the visible light region (e.g., light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (e.g., light with a wavelength of 800 to 1,300 nm).

[0278] The color filter 112 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light range, and for example, a color filter formed with red (R), green (G), and blue (B) pixels is used.

[0279] Between the infrared transmission filter 113 and the solid-state imaging element 110, a resin film 114 that is capable of transmitting light of the wavelength that has passed through the infrared transmission filter 113 is disposed.

[0280] The infrared transmission filter 113 is formed from the cured product of the present disclosure, has visible light blocking properties, and transmits infrared light of a specific wavelength. The infrared transmission filter 113 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1,300 nm, for example.

[0281] A microlens 115 is disposed on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed to cover the microlens 115.

[0282] In the embodiment shown in FIG. 4, the resin film 114 is disposed, but the infrared transmission filter 113 may be formed instead of the resin film 114 .

[0283] This infrared sensor can simultaneously capture image information, enabling motion sensing that recognizes the movement of an object. Furthermore, this infrared sensor can acquire distance information, enabling the capture of images that include 3D information. Furthermore, this infrared sensor can also be used as a biometric authentication sensor.

[0284] In the infrared sensor 120 shown in FIG. 4 , the infrared cut filter 111 and the infrared transmission filter 113 are made of a cured product of the photosensitive resin composition of the present disclosure, but other components (e.g., the resin film 114, the microlens 115, the planarization film 116, and the color filter 112) may be made of a cured product of the photosensitive resin composition of the present disclosure. In this case, the infrared cut filter 111 and the infrared transmission filter 113 may be made of a cured product other than the photosensitive resin composition of the present disclosure. Furthermore, only one of the infrared cut filter 111 and the infrared transmission filter 113 may be made of a cured product of the photosensitive resin composition of the present disclosure.

[0285] Examples that more specifically disclose embodiments of the present disclosure are shown below. Note that the present disclosure is not limited to these examples. Furthermore, all pressures shown below are absolute pressures.

[0286] In the examples, unless otherwise specified, some compounds are represented as follows:

[0287] NB: 2-norbornene PCy ３ : Tricyclohexylphosphine (purchased from TCI) PGMEA: Propylene glycol monomethyl ether acetate CHX: Cyclohexanone TMAH: Tetramethylammonium hydroxide

[0288] BTHB-NB: A compound represented by the following chemical formula (manufactured by Central Glass Co., Ltd.)

[0289] 4FHB-NB: A compound represented by the following chemical formula

[0290] PEG-NB (5-{[2-(2-methoxyethoxy)ethoxy]methyl}bicyclo[2.2.1]hept-2-ene), Mw 226.31: a compound represented by the following chemical formula

[0291] 4FHP-NB: A compound represented by the following chemical formula

[0292] 4FHB-4FA-NB: a compound represented by the following chemical formula

[0293] ME-4FHB-NB: A compound represented by the following chemical formula

[0294] Grubbs catalyst M720: a compound represented by the following chemical formula (purchased from Aldrich)

[0295] Pd(dba) ２ : A compound represented by the following chemical formula (bisdibenzylideneacetone palladium) (purchased from TCI)

[0296] TTPB (triphenylmethylium tetrakis(pentafluorophenyl)borate): a compound represented by the following chemical formula (purchased from TCI)

[0297] DNQ1 (NT200): A compound represented by the following chemical formula (purchased from Toyo Gosei Co., Ltd.)

[0298] DNQ2 (TKF528): A compound represented by the following chemical formula (purchased from Sanbo Chemical Co., Ltd.)

[0299] EOCN-1020-55 (cresol novolac epoxy): a compound represented by the following chemical formula (purchased from Nippon Kayaku Co., Ltd.)

[0300] CPI-210S (photoacid generator): Compound represented by the following chemical formula (purchased from San-Apro Co., Ltd.)

[0301] The equipment used for various measurements and the measurement conditions will be explained.

[0302] [Analysis of Monomer] A nuclear magnetic resonance spectrometer (hereinafter referred to as NMR, manufactured by JEOL Ltd., equipment name JNM-ECA400) with a resonance frequency of 400 MHz was used. １９ F-NMR, １ H-NMR was measured.

[0303] [Polymer Analysis] The content of each unit in the polymer was determined by NMR. １ H-NMR and １９ It was determined by F-NMR measurements.

[0304] [Molecular Weight Analysis] The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the polymer were measured using high performance gel permeation chromatography (hereinafter sometimes referred to as GPC, manufactured by Tosoh Corporation, Model HLC-8420GPC) with one ALPHA-M column and one ALPHA-2500 column, both manufactured by Tosoh Corporation, connected in series, using tetrahydrofuran as the developing solvent. A refractive index difference detector was used as the detector. A molecular weight calibration curve was prepared using polystyrene as a standard.

[0305] The synthesis of the monomer will be explained.

[0306] [Synthesis Example 1-1: Synthesis of 4FHB] 1,3-dichlorotetrafluoroacetone (50 g, 0.25 mol, manufactured by Synquest Laboratories) was charged into a pressure-resistant vessel (500 ml) equipped with a stirrer, and the reactor was sealed. Next, the reactor was degassed using a vacuum pump, and then 10.5 g (0.25 mol) of propylene was introduced while stirring the contents with a stirrer. Next, the temperature inside the reactor was raised to 100°C, and stirring was continued for 80 hours. After completion of the reaction, the mixture was distilled under reduced pressure at a pressure of 3.0 kPa and a temperature of 68°C to 69°C, and 36.5 g of 1-chloro-2-(chlorodifluoromethyl)-1,1-difluoro-3-buten-1-ol (hereinafter referred to as 4FHB) represented by the following formula was obtained in a yield of 60%. This reaction is shown below. <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３, reference material: TMS) δ2.88 (dd, 2H), 3.20 (brs, 1H), 5.34 (dq, 1H), 5.40 (ddt, 1H), 5.89 (m, 1H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-59.7 (s, 4F)

[0307] Synthesis Example 1-2: Synthesis of 4FHB-NB Dicyclopentadiene (13.22 g, 0.1 mol) and 4FHB (24.3 g, 0.1 mol) were charged into a 100 mL SUS autoclave. The reaction mixture was stirred for 1 hour and heated at 150°C for 10 hours. After cooling the reaction mixture, each component was fractionated. The fraction distilled at a pressure of 0.1 kPa and a temperature of 85°C to 90°C was collected to obtain 15 g of 4FHB-NB shown below in a yield of 40%. This reaction is shown below. <NMR Analysis Results> １ H-NMR (CDCl ３ , reference material: TMS) δ0.7 (dd, 1H), 1.20-1.50 (m, 2H), 1.80 (d, 1H), 1.90-2.10 (dd , 2H), 2.81 (m, 1H), 2.92 (m, 1H), 3.05 (m, 1H), 5.98 (dd, 1H), 6.20 (dd, 1H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-59.9 (m, 2F), -60.5 (m, 2F)

[0308] Synthesis Example 2-1: Synthesis of 4FHP A pressure-resistant vessel (1000 ml) equipped with a stirrer was charged with 1,3-dichlorotetrafluoroacetone (Synquest Laboratories, 50 g, 0.25 mol) and 100 ml of THF, and the reactor was sealed. Next, after cooling to -78°C, 250 g (0.25 mol) of a 14% by weight vinyl magnesium bromide THF solution was introduced over 3 hours at an internal temperature of -60 to -78°C while stirring the contents with a stirrer. The temperature was raised to room temperature over 2 hours, and then stirred for 3 hours. After completion of the reaction, the contents were extracted and transferred to a separatory funnel, and 300 ml of 5% by weight hydrochloric acid was added. After stirring for 2 hours, the organic layer and aqueous layer were separated. 50 ml of 4% by weight aqueous sodium hydroxide was added to the organic layer, and after stirring for 1 hour, the organic layer was separated, and the resulting organic layer was concentrated by distilling off the solvent under reduced pressure. The residue was distilled under reduced pressure at a pressure of 3.0 kPa and a temperature of 65 to 67°C to obtain 22.8 g of 1-chloro-2-(chlorodifluoromethyl)-1,1-difluoro-2-propen-1-ol (hereinafter referred to as 4FHP) represented by the following formula in a yield of 40%. The reaction is shown below. <NMR analysis results> １ H-NMR (CDCl ３ , reference material: TMS) δ3.40 (brs, 1H), 5.44 (dq, 1H), 5.50 (ddt, 1H), 5.85 (m, 1H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-59.3 (s, 4F)

[0309] Synthesis Example 2-2: Synthesis of 4FHP-NB Dicyclopentadiene (13.22 g, 0.1 mol) and 4FHP (22.8 g, 0.1 mol) were charged into a 100 mL SUS autoclave. The reaction mixture was stirred for 1 hour and heated at 170°C for 10 hours. After cooling the reaction mixture, each component was fractionated. The fraction distilled at a pressure of 0.1 kPa and a temperature of 83°C to 87°C was collected to obtain 12 g of 4FHP-NB shown below in a yield of 35%. This reaction is shown below. <NMR Analysis Results> １ H-NMR (CDCl ３, reference material: TMS) δ0.72 (dd, 1H), 1.21-1.45 (m, 2H), 1.78 (d, 1H), 2.81 (m, 1H), 2.92 (m, 1H), 3.05 (m, 1H), 5.98 (dd, 1H), 6.20 (dd, 1H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-59.4 (m, 2F), -60.1 (m, 2F)

[0310] Synthesis Example 3-1: Synthesis of 4FHB-4FA 1,3-dichlorotetrafluoroacetone (50 g, 0.25 mol, manufactured by Synquest Laboratories) was charged into a pressure-resistant vessel (500 ml) equipped with a stirrer, and the reactor was sealed. 24.3 g (0.1 mol) of 4FHB synthesized in Synthesis Example 1-1 was introduced. Next, the temperature inside the reactor was raised to 100°C, and stirring was continued for 80 hours. After completion of the reaction, the mixture was distilled under reduced pressure at a pressure of 1.0 kPa and a temperature of 100°C to 103°C, yielding 28.7 g of 4FHB-4FA represented by the following formula in a yield of 65%. This reaction is shown below. <NMR Analysis Results> １ H-NMR (CDCl ３ , reference material: TMS) δ2.95 (m, 2H), 3.20 (brs, 2H), 5.34 (d, 1H), 5.89 (d, 1H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-59.7 (s, 4F), -59.1 (s, 4F)

[0311] Synthesis Example 3-2: Synthesis of 4FHB-4FA-NB Dicyclopentadiene (13.22 g, 0.1 mol) and 4FHB-4FA (22.15 g, 0.05 mol) were charged into a 100 mL SUS autoclave. The reaction mixture was stirred for 1 hour and heated at 150°C for 40 hours. After cooling the reaction mixture, each component was fractionated. The fraction distilled at a pressure of 0.1 kPa and a temperature of 130°C to 140°C was collected to obtain 14.4 g of 4FHB-4FA-NB shown below in a yield of 25%. This reaction is shown below. <NMR Analysis Results> １ H-NMR (CDCl３ , reference material: TMS) δ0.7 (dd, 1H), 1.20-1.25 (m, 1H), 1.83 (d, 1H), 1.92-2.13 (dd , 2H), 2.81 (m, 1H), 2.92 (m, 1H), 3.01 (m, 1H), 5.98 (dd, 1H), 6.24 (dd, 1H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-59.3 (m, 2F), -59.9 (m, 2F), -60.5 (m, 2F), -60.8 (m, 2F)

[0312] Synthesis Example 4-1: Synthesis of ME-4FHB A pressure-resistant vessel (500 ml) equipped with a stirrer was charged with 1,3-dichlorotetrafluoroacetone (Synquest Laboratories, 50 g, 0.25 mol), and the reactor was sealed. Next, the reactor was degassed using a vacuum pump, and then 12.0 g (0.25 mol) of isoprene was introduced while stirring the contents with a stirrer. Next, the temperature inside the reactor was raised to 100°C, and stirring was continued for 80 hours. After completion of the reaction, the mixture was distilled under reduced pressure at a pressure of 3.0 kPa and a temperature of 68°C to 69°C, and 41.8 g of 1-chloro-2-(chlorodifluoromethyl)-1,1-difluoro-3-methyl-3-buten-1-ol (hereinafter referred to as ME-4FHB) represented by the following formula was obtained in a yield of 65%. This reaction is shown below. <NMR analysis results> １ H-NMR (CDCl ３ , reference material: TMS) δ2.20 (s, 3H), 2.85 (dd, 2H), 3.10 (brs, 1H), 5.45 (d, 1H), 5.98 (d, 1H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-59.1 (s, 4F)

[0313] Synthesis Example 4-2: Synthesis of ME-4FHB-NB Dicyclopentadiene (13.22 g, 0.1 mol) and ME-4FHB (25.7 g, 0.1 mol) were charged into a 100 mL SUS autoclave. The reaction mixture was stirred for 1 hour and heated at 150°C for 50 hours. The reaction mixture was cooled and then fractionated to each component. The fractions distilled at a pressure of 0.1 kPa and a temperature of 87°C to 93°C were collected to obtain 13.6 g of ME-4FHB-NB shown below in a yield of 35%. This reaction is shown below. <NMR Analysis Results> １ H-NMR (CDCl ３ , reference material: TMS) δ0.72 (dd, 1H), 1.24-1.51 (m, 2H), 1.75 (d, 1H), 1.81 (s, 3H), 1.93-2.15 (dd, 2H), 2.89 (m, 1H), 3.01 (m, 1H), 5.92 (dd, 1H), 6.11 (dd, 1H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-60.9 (m, 2F), -61.5 (m, 2F)

[0314] [Synthesis Example 5: Synthesis of trioxanonanylnorbornene (PEG-NB)] Synthesis was performed according to Example A26 (synthesis of trioxanonanylnorbornene) described in WO 2012 / 028278, and the target PEG-NB was obtained with a gas chromatography purity of 99%.

[0315] Next, the synthesis of the polymer will be described.

[0316] [Polymer Synthesis Example 1] (Synthesis of 4FHB-NB Metathesis Polymer, Mw 10k: Metathesis Polymer 1) Grubbs catalyst M720 (18.8 mg, 0.03 mmol) was placed in a dried three-neck 200 ml flask and purged with nitrogen. 30 ml of anhydrous toluene was added to the flask and stirred at room temperature to uniformly dissolve the catalyst. To this solution, a mixture of 4FHB-NB (18.43 g, 60 mmol), 1-hexene (0.38 g, 4.5 mmol), and 30 ml of anhydrous toluene was added via syringe. The mixture was stirred overnight at room temperature to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by suction filtration, yielding a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator, and the concentrated solid was dissolved in 50 g of methanol. The methanol solution was poured into 500 g of water to obtain a white viscous solid. This viscous solid was dried under reduced pressure at 60° C. to obtain a solid metathesis polymer 1 (Mw 10k, dispersity 1.75) in a yield of 12.80 g.

[0317] [Polymer Synthesis Example 2] (Synthesis of BTHB-NB Metathesis Polymer, Mw 10k: Metathesis Polymer 2) Grubbs catalyst M720 (18.8 mg, 0.03 mmol) was placed in a dried three-necked 200 ml flask and purged with nitrogen. 30 ml of anhydrous toluene was added to the flask and stirred at room temperature to uniformly dissolve the catalyst. To this solution, a mixture of BTHB-NB (16.45 g, 60 mmol), 1-hexene (0.38 g, 4.5 mmol), and 30 ml of anhydrous toluene was added via syringe. The mixture was stirred overnight at room temperature to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by suction filtration to obtain a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator. The concentrated solid was dissolved in 50 g of methanol, and the methanol solution was poured into 500 g of water to obtain a white viscous solid. This viscous solid was dried under reduced pressure at 60° C. to obtain a solid metathesis polymer 2 (Mw 10k, dispersity 1.81) in a yield of 14.57 g.

[0318] [Polymer Synthesis Example 3] (Synthesis of PEG-NB Metathesis Polymer, Mw 10k: Metathesis Polymer 3) Grubbs catalyst M720 (18.8 mg, 0.03 mmol) was placed in a dried three-necked 200 ml flask and purged with nitrogen. 30 ml of anhydrous toluene was added to the flask and stirred at room temperature to uniformly dissolve the catalyst. To this solution, a mixture of PEG-NB (13.58 g, 60 mmol), 1-hexene (0.38 g, 4.5 mmol), and 30 ml of anhydrous toluene was added via syringe. The mixture was stirred overnight at room temperature to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by suction filtration to obtain a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator, and the concentrated solid was dissolved in 50 g of methanol. The methanol solution was poured into 500 g of water to obtain a white viscous solid. This viscous solid was dried under reduced pressure at 60° C. to obtain a solid metathesis polymer 3 (Mw 10k, dispersity 1.90) in a yield of 10.01 g.

[0319] [Polymer Synthesis Example 4] (Synthesis of 4FHB-NB / NB=1 / 1 metathesis polymer, Mw 10k: Metathesis Polymer 4) Grubbs catalyst M720 (18.8 mg, 0.03 mmol) was placed in a dried three-necked 200 ml flask and purged with nitrogen. 30 ml of dehydrated toluene was added to the flask and stirred at room temperature to uniformly dissolve the catalyst. To this solution, a mixture of 4FHB-NB (9.21 g, 30 mmol), NB (2.82 g, 30 mmol), 1-hexene (0.50 g, 6.0 mmol), and 30 ml of dehydrated toluene was added via syringe. The mixture was stirred overnight at room temperature to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by suction filtration, yielding a pale yellow treated solution. The resulting solution was concentrated using a rotary evaporator, and the concentrated solid was dissolved in 50 g of methanol. The methanol solution was poured into 500 g of water to obtain a white viscous solid. The viscous solid was dried under reduced pressure at 60° C. to obtain a solid metathesis polymer 4 (Mw 10k, dispersity 2.01) in a yield of 8.99 g.

[0320] [Polymer Synthesis Example 5] (Synthesis of BTHB-NB / NB=1 / 1 metathesis polymer, Mw 10k: Metathesis Polymer 5) Grubbs catalyst M720 (18.8 mg, 0.03 mmol) was placed in a dried three-necked 200 ml flask and purged with nitrogen. 30 ml of dehydrated toluene was added to the flask and stirred at room temperature to uniformly dissolve the catalyst. To this solution, a mixture of BTHB-NB (8.23 g, 30 mmol), NB (2.82 g, 30 mmol), 1-hexene (0.50 g, 6.0 mmol), and 30 ml of dehydrated toluene was added via syringe. The mixture was stirred overnight at room temperature to obtain a reaction solution. 2 g of activated carbon was added to the obtained reaction solution, and after stirring for 2 hours, the activated carbon was removed by suction filtration, yielding a pale yellow treated solution. The resulting solution was concentrated using a rotary evaporator, and the concentrated solid was dissolved in 50 g of methanol. The methanol solution was poured into 500 g of water to obtain a white viscous solid. The viscous solid was dried under reduced pressure at 60° C. to obtain 7.43 g of a solid metathesis polymer 5 (Mw 10k, dispersity 1.99).

[0321] [Polymer Synthesis Example 6] (4FHB-NB Coordination Addition Polymer: Coordination Addition Polymer 1) Pd(dba) ２ (115.0 mg, 0.2 mmol), TTPB (184.5 mg, 0.2 mmol), PCy ３ (56.1 mg, 0.2 mmol) was added and the atmosphere was purged with nitrogen. 50 ml of dehydrated toluene was added to the flask, and the catalyst was uniformly dissolved by stirring at room temperature. A mixture of 4FHB-NB (6.14 g, 20 mmol) and 50 ml of dehydrated toluene was added to this solution via syringe. The mixture was stirred overnight at 35°C to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by filtration through Celite to obtain a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator, and the concentrated solid was dissolved in 20 g of acetone. This acetone solution was poured into 200 g of heptane to obtain a white solid. This solid was dried under reduced pressure at 60°C to obtain a solid coordination addition polymerization polymer 1 (Mw 76 kJ, dispersity 1.08) in a yield of 3.09 g.

[0322] Polymer Synthesis Example 7 (BTHB-NB Coordination Addition Polymer: Coordination Addition Polymer 2) Pd(dba) was placed in a dry three-neck 300 ml flask. ２ (115.0 mg, 0.2 mmol), TTPB (184.5 mg, 0.2 mmol), PCy ３ (56.1 mg, 0.2 mmol) was added and the atmosphere was purged with nitrogen. 50 ml of dehydrated toluene was added to the flask, and the catalyst was uniformly dissolved by stirring at room temperature. A mixture of BTHB-NB (5.48 g, 20 mmol) and 50 ml of dehydrated toluene was added to this solution via syringe. The mixture was stirred overnight at 35°C to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by filtration through Celite to obtain a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator, and the concentrated solid was dissolved in 20 g of acetone. This acetone solution was poured into 200 g of heptane to obtain a white solid. This solid was dried under reduced pressure at 60°C to obtain 2.16 g of solid coordination addition polymerization polymer 2 (Mw 69 kJ, dispersity 1.08).

[0323] [Polymer Synthesis Example 8] (Synthesis of PEG-NB Coordination Addition Polymer: Coordination Addition Polymer 3) Pd(dba) was placed in a dry three-neck 300 ml flask. ２ (115.0 mg, 0.2 mmol), TTPB (184.5 mg, 0.2 mmol), PCy ３ (56.1 mg, 0.2 mmol) was added and the atmosphere was purged with nitrogen. 50 ml of dehydrated toluene was added to the flask, and the catalyst was uniformly dissolved by stirring at room temperature. A mixture of PEG-NB (4.53 g, 20 mmol) and 50 ml of dehydrated toluene was added to this solution via syringe. The mixture was stirred overnight at 35°C to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by filtration through Celite to obtain a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator, and the concentrated solid was dissolved in 20 g of acetone. This acetone solution was poured into 200 g of heptane to obtain a white solid. This solid was dried under reduced pressure at 60°C to obtain 1.58 g of solid coordination addition polymerization polymer 3 (Mw 88k, dispersity 1.12).

[0324] [Polymer Synthesis Example 9] (Synthesis of 4FHP-NB Metathesis Polymer, Mw 11k: Metathesis Polymer 6) Grubbs catalyst M720 (18.8 mg, 0.03 mmol) was placed in a dried three-neck 200 ml flask and purged with nitrogen. 30 ml of anhydrous toluene was added to the flask and stirred at room temperature to uniformly dissolve the catalyst. To this solution, a mixture of 4FHP-NB (17.58 g, 60 mmol), 1-hexene (0.38 g, 4.5 mmol), and 30 ml of anhydrous toluene was added via syringe. The mixture was stirred overnight at room temperature to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by suction filtration to obtain a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator. The concentrated solid was dissolved in 50 g of methanol, and the methanol solution was poured into 500 g of water to obtain a white viscous solid. This viscous solid was dried under reduced pressure at 60° C. to obtain a solid metathesis polymer 6 (Mw 11k, dispersity 1.73) in a yield of 12.11 g.

[0325] [Polymer Synthesis Example 10] (Synthesis of 4FHB-4FA-NB metathesis polymer, Mw 10k: Metathesis Polymer 7) Grubbs catalyst M720 (18.8 mg, 0.03 mmol) was placed in a dried three-neck 200 ml flask and purged with nitrogen. 30 ml of anhydrous toluene was added to the flask and stirred at room temperature to uniformly dissolve the catalyst. To this solution, a mixture of 4FHB-4FA-NB (29.65 g, 60 mmol), 1-hexene (0.38 g, 4.5 mmol), and 30 ml of anhydrous toluene was added via syringe. The mixture was stirred overnight at room temperature to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by suction filtration to obtain a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator. The concentrated solid was dissolved in 50 g of methanol, and the methanol solution was poured into 500 g of water to obtain a white viscous solid. This viscous solid was dried under reduced pressure at 60° C. to obtain a solid metathesis polymer 7 (Mw 10k, dispersity 1.79) in a yield of 26.13 g.

[0326] [Polymer Synthesis Example 11] (Synthesis of ME-4FHB-NB Metathesis Polymer, Mw 11k: Metathesis Polymer 8) Grubbs catalyst M720 (18.8 mg, 0.03 mmol) was placed in a dried three-neck 200 ml flask and purged with nitrogen. 30 ml of anhydrous toluene was added to the flask and stirred at room temperature to uniformly dissolve the catalyst. To this solution, a mixture of ME-4FHB-NB (19.32 g, 60 mmol), 1-hexene (0.38 g, 4.5 mmol), and 30 ml of anhydrous toluene was added via syringe. The mixture was stirred overnight at room temperature to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by suction filtration to obtain a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator, and the concentrated solid was dissolved in 50 g of methanol. The methanol solution was poured into 500 g of water to obtain a white viscous solid. This viscous solid was dried under reduced pressure at 60° C. to obtain a solid metathesis polymer 8 (Mw 11k, dispersity 1.74) in a yield of 16.54 g.

[0327] Polymer Synthesis Example 12 (4FHP-NB Coordination Addition Polymer: Coordination Addition Polymer 4) Pd(dba) was placed in a dry three-neck 300 ml flask. ２ (115.0 mg, 0.2 mmol), TTPB (184.5 mg, 0.2 mmol), PCy ３ (56.1 mg, 0.2 mmol) was added and the atmosphere was purged with nitrogen. 50 ml of dehydrated toluene was added to the flask, and the catalyst was uniformly dissolved by stirring at room temperature. A mixture of 4FHP-NB (5.86 g, 20 mmol) and 50 ml of dehydrated toluene was added to this solution via syringe. The mixture was stirred overnight at 35°C to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by filtration through Celite, yielding a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator, and the concentrated solid was dissolved in 20 g of acetone. This acetone solution was poured into 200 g of heptane to obtain a white solid. This solid was dried under reduced pressure at 60°C to obtain 2.89 g of solid coordination addition polymerization polymer 4 (Mw 81k, dispersity 1.11).

[0328] Polymer Synthesis Example 13 (4FHB-4FA-NB Coordination Addition Polymer: Coordination Addition Polymer 5) Pd(dba) was placed in a dry three-neck 300 ml flask. ２ (115.0 mg, 0.2 mmol), TTPB (184.5 mg, 0.2 mmol), PCy ３ (56.1 mg, 0.2 mmol) was added and the atmosphere was purged with nitrogen. 50 ml of dehydrated toluene was added to the flask, and the catalyst was uniformly dissolved by stirring at room temperature. A mixture of 4FHB-4FA-NB (9.88 g, 20 mmol) and 50 ml of dehydrated toluene was added to this solution via syringe. The mixture was stirred overnight at 35°C to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by filtration through Celite to obtain a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator, and the concentrated solid was dissolved in 20 g of acetone. This acetone solution was poured into 200 g of heptane to obtain a white solid. This solid was dried under reduced pressure at 60°C to obtain a solid coordination addition polymerization polymer 5 (Mw 72k, dispersity 1.12) in a yield of 8.16 g.

[0329] Polymer Synthesis Example 14 (Synthesis of ME-4FHB-NB Coordination Addition Polymer: Coordination Addition Polymer 6) Pd(dba) was placed in a dry three-neck 300 ml flask. ２ (115.0 mg, 0.2 mmol), TTPB (184.5 mg, 0.2 mmol), PCy ３ (56.1 mg, 0.2 mmol) was added and the atmosphere was purged with nitrogen. 50 ml of dehydrated toluene was added to the flask, and the catalyst was uniformly dissolved by stirring at room temperature. To this solution, a mixture of ME-4FHB-NB (6.44 g, 20 mmol) and 50 ml of dehydrated toluene was added via syringe. The mixture was stirred overnight at 35°C to obtain a reaction solution. 2 g of activated carbon was added to the resulting reaction solution, and after stirring for 2 hours, the activated carbon was removed by filtration through Celite to obtain a pale yellow treated solution. The resulting treated solution was concentrated using a rotary evaporator, and the concentrated solid was dissolved in 20 g of acetone. This acetone solution was poured into 200 g of heptane to obtain a white solid. This solid was dried under reduced pressure at 60°C to obtain a solid coordination addition polymerization polymer 6 (Mw 81k, dispersity 1.10) in a yield of 4.51 g.

[0330] Example 1 0.1 g of metathesis polymer 1, 0.02 g of DNQ2 (TKF528), and 0.9 g of CHX were dissolved in a 5 ml vial to obtain coating solution 1. Using a Mikasa spin coater, coating solution 1 was spin-coated onto a 4-inch silicon wafer at 1000 rpm, and the wafer was dried on a hot plate at 100°C for 3 minutes to obtain coating film 1. This coating film 1 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0331] Example 2 0.1 g of metathesis polymer 1, 0.005 g of DNQ2 (TKF528), and 0.9 g of PGMEA were added to a 5 ml vial and dissolved with , to obtain coating solution 2. Coating solution 2 was spin-coated onto a 4-inch silicon wafer at 1000 rpm, and dried on a hot plate at 100°C for 3 minutes to obtain coating film 2. This coating film 2 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0332] Example 3 0.1 g of metathesis polymer 1, 0.01 g of DNQ1 (NT200), and 0.9 g of PGMEA were dissolved in a 5 ml vial to obtain coating solution 3. Coating solution 3 was spin-coated onto a 4-inch silicon wafer at 1000 rpm, and dried on a hot plate at 100°C for 3 minutes to obtain coating film 3. This coating film 3 was observed using a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with an ◯, and if observed, it was marked with an ×. The results are shown in Table 1. A microscopic photograph of the surface of coating film 3 obtained in Example 3 is shown in Figure 5.

[0333] Example 4 0.1 g of metathesis polymer 1, 0.02 g of an epoxy crosslinker (EOCN-1020-55), and 0.9 g of PGMEA were dissolved in a 5 ml vial to obtain coating solution 4. Coating solution 4 was spin-coated onto a 4-inch silicon wafer at 1000 rpm, and dried on a hot plate at 100°C for 3 minutes to obtain coating film 4. This coating film 4 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a "good"; if neither unevenness nor layer separation was observed, it was marked with an "x." The results are shown in Table 1.

[0334] Example 5 0.1 g of coordination addition polymerization polymer 1, 0.01 g of DNQ1 (NT200), and 0.9 g of PGMEA were dissolved in a 5 ml vial to obtain coating solution 5. Coating solution 5 was spin-coated onto a 4-inch silicon wafer at 1000 rpm and dried on a hot plate at 100°C for 3 minutes to obtain coating film 5. This coating film 5 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0335] Example 6 Coating Solution 6 was obtained by the same procedure as in Example 3, except that Metathesis Polymer 1 was replaced with Metathesis Polymer 4. Coating Solution 6 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain Coating Film 6. This Coating Film 6 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if neither unevenness nor layer separation was observed, it was marked with an X. The results are shown in Table 1.

[0336] Example 7 0.1 g of coordination addition polymerization polymer 1, 0.02 g of an epoxy crosslinker (EOCN-1020-55), and 0.9 g of PGMEA were added to a 5 ml vial and dissolved to obtain coating solution 7. Coating solution 7 was spin-coated onto a 4-inch silicon wafer at 1000 rpm, and dried on a hot plate at 100°C for 3 minutes to obtain coating film 7. This coating film 7 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with ◯, and if observed, it was marked with ×. The results are shown in Table 1.

[0337] Example 8 Coating Solution 17 was obtained by the same procedure as in Example 3, except that Metathesis Polymer 1 was replaced with Metathesis Polymer 6. Coating Solution 6 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain Coating Film 17. Coating Film 17 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0338] Example 9 Coating solution 18 was obtained by the same procedure as in Example 3, except that metathesis polymer 1 was replaced with metathesis polymer 7. Coating solution 18 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain coating film 18. This coating film 18 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an ×. The results are shown in Table 1.

[0339] Example 10 Coating Solution 19 was obtained by the same procedure as in Example 3, except that Metathesis Polymer 1 was replaced with Metathesis Polymer 8. Coating Solution 19 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain Coating Film 19. Coating Film 19 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0340] Example 11 Coating solution 20 was obtained by the same procedure as in Example 1, except that metathesis polymer 1 was replaced with metathesis polymer 6. Coating solution 20 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain a coating film 20. This coating film 20 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if neither unevenness nor layer separation was observed, it was marked with an X. The results are shown in Table 1.

[0341] Example 12 Coating solution 21 was obtained by the same procedure as in Example 1, except that metathesis polymer 1 was replaced with metathesis polymer 7. Coating solution 21 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain coating film 21. This coating film 21 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0342] Example 13 Coating solution 22 was obtained by the same procedure as in Example 1, except that metathesis polymer 1 was replaced with metathesis polymer 8. Coating solution 22 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain coating film 22. This coating film 22 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0343] Example 14 Coating Solution 23 was obtained by the same procedure as in Example 4, except that Metathesis Polymer 1 was replaced with Metathesis Polymer 6. Coating Solution 23 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain Coating Film 23. This Coating Film 23 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0344] Example 15 Coating solution 24 was obtained by the same procedure as in Example 4, except that metathesis polymer 1 was replaced with metathesis polymer 7. Coating solution 24 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and dried on a hot plate at 100°C for 3 minutes to obtain coating film 24. This coating film 24 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an ×. The results are shown in Table 1.

[0345] Example 16 Coating Solution 25 was obtained by the same procedure as in Example 4, except that Metathesis Polymer 1 was replaced with Metathesis Polymer 8. Coating Solution 25 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain Coating Film 25. This Coating Film 25 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0346] Example 17 Coating solution 26 was obtained by the same procedure as in Example 3, except that the metathesis polymer 1 was replaced with coordination addition polymerization polymer 4. Coating solution 26 was spin-coated onto a 4-inch silicon wafer at 1000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain coating film 26. This coating film 26 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0347] Example 18 Coating Solution 27 was obtained by the same procedure as in Example 3, except that the metathesis polymer 1 was replaced with coordination addition polymerization polymer 5. Coating Solution 27 was spin-coated onto a 4-inch silicon wafer at 1000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain Coating Film 27. Coating Film 27 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0348] Example 19 Coating solution 28 was obtained by the same procedure as in Example 3, except that the metathesis polymer 1 was replaced with coordination addition polymerization polymer 6. Coating solution 28 was spin-coated onto a 4-inch silicon wafer at 1000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain coating film 28. This coating film 28 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0349] Comparative Examples 1 to 4 Coating Solutions 8 to 11 were obtained by the same procedure as in Examples 1 to 4, except that Metathesis Polymer 1 was replaced with Metathesis Polymer 2. Coating Solutions 8 to 11 were spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes, yielding Coating Films 8 to 11. These Coating Films 8 to 11 were observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, the result was rated as ◯, and if observed, an ×. The results are shown in Table 1. A microscopic photograph of the surface of Coating Film 10 obtained in Comparative Example 3 is shown in FIG. 6.

[0350] Comparative Example 5 Coating solution 12 was obtained by the same procedure as in Example 5, except that the coordination addition polymerization polymer 1 was replaced with coordination addition polymerization polymer 2. Coating solution 12 was spin-coated onto a 4-inch silicon wafer at 1000 rpm, and dried on a hot plate at 100°C for 3 minutes to obtain coating film 12. This coating film 12 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an ×. The results are shown in Table 1.

[0351] Comparative Example 6 Coating Solution 13 was obtained by the same procedure as in Example 3, except that Metathesis Polymer 1 was replaced with Metathesis Polymer 3. Coating Solution 13 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain Coating Film 13. This Coating Film 13 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0352] Comparative Example 7 Coating Solution 14 was obtained by the same procedure as in the preparation of Coating Solution 5, except that Coordination Addition Polymerization Polymer 1 was changed to Coordination Addition Polymerization Polymer 3. Coating Solution 14 was spin-coated onto a 4-inch silicon wafer at 1000 rpm, and dried on a hot plate at 100°C for 3 minutes to obtain Coating Film 14. This Coating Film 14 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0353] Comparative Example 8 Coating Solution 15 was obtained by the same procedure as in Example 3, except that Metathesis Polymer 1 was replaced with Metathesis Polymer 5 in the coating solution preparation method. Coating Solution 15 was spin-coated onto a 4-inch silicon wafer at 1,000 rpm, and then dried on a hot plate at 100°C for 3 minutes to obtain Coating Film 15. This Coating Film 15 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with a circle, and if observed, it was marked with an X. The results are shown in Table 1.

[0354] Comparative Example 9 0.1 g of coordination addition polymerization polymer 2, 0.02 g of an epoxy crosslinker (EOCN-1020-55), and 0.9 g of PGMEA were added to a 5 ml vial and dissolved to obtain coating solution 16. Coating solution 16 was spin-coated onto a 4-inch silicon wafer at 1000 rpm, and dried on a hot plate at 100°C for 3 minutes to obtain coating film 16. This coating film 16 was observed with a Keyence microscope to check for unevenness or layer separation. If no unevenness or layer separation was observed, it was marked with ◯, and if observed, it was marked with ×. The results are shown in Table 1.

[0355]

[0356] From Table 1, it can be seen that the examples using polymers having units derived from the compound represented by the general formula (1) have excellent coating film appearances and excellent compatibility. Furthermore, from a comparison of Figures 5 and 6, it can be seen that the examples using polymers having units derived from the compound represented by the general formula (1) have clearly excellent coating film appearances and very excellent compatibility.

[0357] [Thermal Stability Test] The 5% weight loss temperatures of metathesis polymers 1 to 8 and coordination addition polymerization polymers 1 to 6 were measured using a TG-DTA manufactured by Hitachi High-Technologies Corporation. The conditions were as follows. A 5% weight loss temperature of 300°C or higher was determined to have good thermal stability. Sample amount: 10 mg Heating program: 30°C to 500°C, heating at 10°C / min Sample pan: Al Atmosphere: N ２ The results are shown in Table 2.

[0358]

[0359] From Table 2, it can be seen that the polymers of the examples having units derived from the compound represented by the general formula (1) have a high 5% weight loss temperature and good thermal stability.

[0360] The results in Tables 1 and 2 reveal that, although a polymer (PEG-NB polymer) having units derived from a norbornene monomer (PEG-NB) having a polyethylene glycol chain in its side chain was synthesized with the aim of improving the compatibility of a BTHB-NB polymer, while compatibility was improved, good thermal stability could not be obtained. Thus, it has become clear that, although a PEG-NB polymer having a polyethylene glycol chain in its side chain and the like loses thermal stability, which is an excellent property of the norbornene skeleton, by using the compound of the present disclosure, a polymer having excellent compatibility can be provided while the excellent properties (e.g., thermal stability) of the norbornene skeleton are fully maintained.

[0361] [Positive Patterning Test] A 4-inch silicon wafer that had been spin-coated with hexamethyldisilazane at 1500 rpm and heat-treated at 200°C for 3 minutes was spin-coated with Coating Solution 3 of Example 3 at 200 rpm, and dried on a hot plate at 100°C for 3 minutes to obtain a coating film 3-2 with a thickness of 1.3 μm. The film thickness was measured by scraping a portion of the coating film down to the substrate with a spatula and observing the step between the substrate and the top of the coating film using a Kosaka Laboratory Microshape Measuring Instrument ET200A-D. This film was patterned using a SUSS Mask Aligner MA-6 with ghi rays irradiated from a high-pressure mercury lamp and a 5 μm / 5 μm line-and-space mask attached, at an exposure dose of 100 mJ / cm. ２Contact exposure was performed at 1000 K. The exposed coating film was immersed in a 2.38% TMAH aqueous solution for 150 seconds, rinsed with pure water, and dried with an air blower. The resulting pattern was observed under a microscope, and it was confirmed that the exposed area had dissolved, leaving a positive pattern with approximately the same dimensions as the mask. The film thickness of the patterned area was 1.2 μm.

[0362] [Negative Patterning Test] A 4-inch silicon wafer was spin-coated with hexamethyldisilazane at 1500 rpm and heated at 200°C for 3 minutes. A solution of 1.02 g of Coating Solution 4 from Example 4 and 0.001 g of a photoacid generator (CPI-210S) was then spin-coated at 200 rpm, and the wafer was dried on a hot plate at 80°C for 1 minute to obtain a coating film 4-2 with a thickness of 1.3 μm. This film was then patterned with a SUSS mask aligner MA-6 using ghi line and a 5 μm / 5 μm line-and-space mask at an exposure dose of 50 mJ / cm. ２ Contact exposure was performed at 80°C. The exposed coating film was heated on a hot plate at 80°C for 1 minute. The heated coating film was immersed in a 2.38% TMAH aqueous solution for 250 seconds, rinsed with pure water, and dried with an air blower. The obtained pattern was observed under a microscope, and it was confirmed that the unexposed areas had dissolved and a negative pattern of approximately the same dimensions as the mask had been drawn. The film thickness of the patterned area was 1.1 μm.

[0363] The results of the positive patterning test and the negative patterning test revealed that a composition containing a polymer having units derived from the compound represented by general formula (1) can be patterned by exposure to light and can be used as a photosensitive composition.

[0364] REFERENCE SIGNS LIST 10 Substrate 12 Counter substrate 14 Liquid crystal layer 20 Insulating film 22 Opening 24 Opening 26 Opening 30 Transistor 31 Gate electrode 32 Source electrode 33 Drain electrode 34 Gate insulating film 35 Semiconductor layer 40 Wiring 42 Wiring 50 Insulating film 52 Insulating film 54 Insulating film 70 Rewiring 72 Top layer wiring 74 Bump 80 Rewiring layer 90 Alignment film 92 Alignment film 100 Electronic device 110 Solid-state imaging element 111 Infrared cut filter 112 Color filter 113 Infrared transmission filter 114 Resin film 115 Microlens 116 Planarization film 120 Infrared sensor 130 Electronic device 200 Chip stack (stacked semiconductor element) 201 Adhesive layer 210 Electronic device 220 Semiconductor chip (semiconductor element) 230 Package substrate 231 Core substrate 232 Insulating layer 233 Solder resist layer 234 Wiring 235 Conductive via 250 Molded portion 270 Bonding wire 280 Solder ball 601 Adhesive layer

Claims

1. A compound represented by the following general formula (1): (In the general formula (1), n ​​is 0, 1 or 2, and R １ ~R ４ are each independently a monovalent substituent, and R １ ~R ４ At least one of the above is a group represented by the following formula (a): (In the general formula (a), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different.) 2. The compound according to claim 1, wherein the group represented by formula (a) is a group represented by the following formula (a-1): (In general formula (a-1), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different.) 3. In general formula (a-1), R ５ The compound according to claim 2, wherein is an alkylene group which may have a single bond, a straight-chain, branched or cyclic structure.

4. In the general formula (a), two CF ｍ Cl （３－ｍ） Both are CF ２ The compound of claim 1, wherein the compound is Cl.

5. The compound according to claim 1, which is a compound represented by the following formula:

6. A polymer having units derived from a compound represented by the following general formula (1): (In the general formula (1), n ​​is 0, 1 or 2, and R １ ~R ４ are each independently a monovalent substituent, and R １ ~R ４ At least one of the above is a group represented by the following formula (a): (In the general formula (a), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different.) 7. The polymer according to claim 6, wherein the group represented by formula (a) is a group represented by the following formula (a-1): (In general formula (a-1), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different.) 8. In general formula (a-1), R ５ 8. The polymer according to claim 7, wherein is an alkylene group which may have a single bond, a straight-chain, a branched or a cyclic structure.

9. In the general formula (a), two CF ｍ Cl （３－ｍ） Both are CF ２ The polymer according to claim 6, wherein the aryl group is Cl.

10. The polymer according to claim 6, wherein the compound represented by the general formula (1) is a compound represented by the following formula:

11. A photosensitive resin composition comprising the polymer according to any one of claims 6 to 10.

12. The photosensitive resin composition according to claim 11, further comprising a naphthoquinone diazide group-containing compound.

13. The photosensitive resin composition according to claim 11, further comprising a crosslinking agent and a photopolymerization initiator.

14. An adhesive comprising the photosensitive resin composition according to claim 11.

15. A cured product obtained by curing the photosensitive resin composition according to claim 11.

16. An electronic device comprising the cured product according to claim 15.

17. The electronic device according to claim 16, wherein the cured product is an adhesive layer, a protective film, an insulating film, and / or a planarizing film.

18. The electronic device according to claim 16, comprising a stacked semiconductor element, the stacked semiconductor element being a semiconductor device having a plurality of semiconductor elements and the cured material provided between the semiconductor elements to bond them together.

19. An electronic device according to claim 16, comprising an optical filter having the cured product.

20. An electronic device according to claim 19, comprising a solid-state image sensor having said optical filter.

21. The electronic device according to claim 19, which is an image display device equipped with the optical filter.

22. A compound represented by the following general formula (10): (In general formula (10), R １１ ~R １４ are each independently a monovalent substituent, and R １１ ~R １４ At least one of the above is a group represented by the following formula (a-1): (In general formula (a-1), m is 1 or 2, and R ５ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. * is a bond. Two CF ｍ Cl （３－ｍ） may be the same or different.) 23. In general formula (a-1), R ５ The compound according to claim 22, wherein is an alkylene group which may have a single bond, a straight-chain, branched or cyclic structure.

24. In general formula (a-1), two CF ｍ Cl （３－ｍ） Both are CF ２ 23. The compound of claim 22, wherein:

25. The compound according to claim 22, which is a compound represented by the following formula:

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