Method for manufacturing polyamide resin

Abstract

To provide a method for producing a polyimide resin capable of producing a polyimide resin having a high molecular weight to a desired degree by polycondensation of a dicarboxylic acid which is a reaction product of a tetracarboxylic dianhydride and alcohols with a diamine compound.SOLUTION: There is provided a method for producing a polyamide resin which comprises producing a polyamide resin by polycondensation of a dicarboxylic acid which is a reaction product of a tetracarboxylic dianhydride and alcohols with a diamine compound, wherein the polycondensation is carried out in the presence of a compound (A) having a pKa value of 5.5 or more and 8.05 or less and a hydroxy group or a thiol group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polyamide resin by polycondensation of a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and alcohols, with a diamine compound. [Background technology]

[0002] Polyimide resins and polyamide resins are widely used as insulating and protective materials in various elements and electrical and electronic components such as multilayer wiring boards and other electronic circuit boards, due to their excellent heat resistance, mechanical strength, insulation properties, and low dielectric constant.

[0003] In recent years, communication devices such as mobile phones have been increasingly using higher frequencies. Therefore, the insulating parts that insulate the metal wiring in these devices also need to be able to handle these higher frequencies. Here, transmission loss increases with increasing frequency, and as transmission loss increases, electrical signals attenuate. Therefore, for resins such as polyimide resins, polyamide resins, and polybenzoxazole resins, further reduction of transmission loss is required in the high-frequency band, in order to cope with higher frequencies, and to further reduce transmission loss.

[0004] Furthermore, when manufacturing various elements and electronic substrates, it is often necessary to form insulating or protective materials only at desired locations. Therefore, there is a need for a photosensitive resin composition that exhibits low dielectric loss tangent and low dielectric constant, and that can form patterned resin films.

[0005] In response to the above requirements, for example, a photosensitive resin composition has been proposed that can form a patterned polyimide resin film, comprising an aromatic polyamide resin having a specific structure having a structural unit derived from 4,4'-bis(4-aminophenoxy)biphenyl and a structural unit derived from a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and an alcohol having a radical polymerizable group such as 2-hydroxyethyl (meth)acrylate, and a photopolymerization initiator (see Patent Document 1, Examples). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2019 / 044874 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, when polyamide resins are produced by polycondensation of a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and alcohols, with a diamine compound using the method described in Patent Document 1, it may be difficult to produce polyamide resins with a desired high molecular weight, or gelation may occur during the production of the polyamide resin.

[0008] The present invention has been made in view of the above problems, and aims to provide a method for producing a polyamide resin in which a polyamide resin with a desired high molecular weight can be produced by polycondensation of a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and alcohols, and a diamine compound. [Means for solving the problem]

[0009] The present inventors have found that the above problems can be solved by a method for producing a polyamide resin, which includes generating a polyamide resin by polycondensation of a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and alcohols, with a diamine compound, in the presence of a compound (A) having a pKa value of 5.5 or more and 8.05 or less, and having a hydroxyl group or a thiol group, and have completed the present invention. More specifically, the present invention provides the following.

[0010] One aspect of the present invention is a method for producing a polyamide resin, comprising generating a polyamide resin by polycondensation of a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and alcohols, and a diamine compound. Polyamide resin is given by the following formula (1): [ka] (In formula (1), X A1 , and Y A1 Each of these is an organic group having 6 to 40 carbon atoms, and R A1 , and R A2 Each of these is an organic group with 3 to 20 carbon atoms. It consists of constituent units represented by, The polycondensation is carried out in the presence of compound (A) having a hydroxyl group or a thiol group. This is a manufacturing method in which the pKa value of compound (A) is between 5.5 and 8.05. [Effects of the Invention]

[0011] According to the present invention, a method for producing polyamide resins with a desired molecular weight can be provided, which involves polycondensation of a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and alcohols, with a diamine compound. [Modes for carrying out the invention]

[0012] ≪Method for producing polyamide resin≫ The method for producing a polyamide resin includes producing a polyamide resin by polycondensing a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and an alcohol, and a diamine compound.

[0013] In this production method, the following formula (1):

Chemical formula

[0014] The polycondensation in the production of the polyamide resin is carried out in the presence of a compound (A) having a hydroxy group or a thiol group. It is a production method in which the pKa value of the compound (A) is 5.5 or more and 8.05 or less.

[0015] According to the above method, by polycondensing a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and an alcohol, and a diamine compound, a polyamide resin with a desired degree of high molecular weight can be produced.

[0016] <Diamine compound> The diamine compound that gives the structural unit represented by formula (1) is represented by the following formula (A2). H2N-Y A1 -NH2 ··· (A2) (In formula (A2), Y A1 represents a divalent organic group having 6 to 40 carbon atoms.)

[0017] Y A1 is a divalent organic group having 6 to 40 carbon atoms. Y A1 may have one or more substituents in addition to the two amino groups. Preferred examples of substituents include fluorine atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, fluorinated alkyl groups having 1 to 6 carbon atoms, fluorinated alkoxy groups having 1 to 6 carbon atoms, carboxyl groups, or hydroxyl groups. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferable that it be a perfluoroalkyl group or a perfluoroalkoxy group.

[0018] Y A1 The lower limit for the number of carbon atoms in the organic group is 6, the upper limit is 40, and 30 is preferred. Y A1 This may be an aliphatic group, but it is preferably an organic group containing one or more aromatic rings.

[0019] Y A1 If the organic group contains one or more aromatic rings, the organic group may be one aromatic group itself, or it may be a group in which two or more aromatic groups are bonded via bonds containing aliphatic hydrocarbon groups and halogenated aliphatic hydrocarbon groups, or heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. A1 Examples of heteroatom-containing bonds, such as oxygen atoms, sulfur atoms, and nitrogen atoms, include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, with -COO-, -O-, -CO-, and -S- being preferred.

[0020] Y that binds to an amino group A1 The aromatic ring inside is preferably a benzene ring. A1 If the ring bonded to the amino group is a condensed ring containing two or more rings, it is preferable that the ring bonded to the amino group in the condensed ring is a benzene ring. Also, Y A1 The aromatic ring contained therein may be an aromatic heterocycle.

[0021] Y A1If the organic group contains an aromatic ring, it is preferable that the organic group is at least one of the groups represented by the following formulas (21) to (24) in order to improve the electrical and mechanical properties of the formed resin film. [ka]

[0022] (21)~(24) Medium, R 111 Q represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a carboxyl group, a sulfonic acid group, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and a halogenated alkyl group having 1 to 4 carbon atoms. In formula (24), Q 1 This refers to the 9,9'-fluorenylidene group, or the formula: -C6H4-, -C6H4-C6H4-, -O-C6H4-C6H4-O-, -O-C6H4-CO-C6H4-O-, -O-C6H4-C(CH3)2-C6H4-O-, -OCO-C6H4-COO-, -OCO-C6H4-C6H4-COO-, -OCO-, -O-, -CO-, -C(CF3)2-, -C(CH3)2-, -CH2-, -O-C6H4-SO2-C6H4-O-, -C(CH3)2-C6H4-C(CH3)2-, -OC 10 H6-O-, -O-C6H4-O-, -O-CH2-O-, and -O-(CH2) n This indicates one selected from the group consisting of groups represented by -O-.

[0023] Q 1 In the example, -C6H4- is a phenylene group, and m-phenylene groups and p-phenylene groups are preferred, with p-phenylene groups being more preferred. Also, -C 10 H6- is a naphthalenediyl group, preferably a naphthalene-1,2-diyl group, a naphthalene-1,4-diyl group, a naphthalene-2,3-diyl group, a naphthalene-2,6-diyl group, and a naphthalene-2,7-diyl group, and more preferably a naphthalene-1,4-diyl group and a naphthalene-2,6-diyl group. Q 1In the example, n is an integer greater than or equal to 1, preferably an integer between 1 and 20, more preferably an integer between 1 and 12, and even more preferably an integer between 1 and 6.

[0024] Y A1 As a diamine compound containing the group represented by formula (24), the compound represented by the following formula (a2) is preferred. For n in formula (a2), Q in formula (24) 1 As explained above. [ka]

[0025] R in equations (21) to (24) 111 From the viewpoint of improving the electrical properties of the formed resin film, hydrogen atoms, fluorine atoms, methyl groups, ethyl groups, or trifluoromethyl groups are more preferred, and hydrogen atoms or trifluoromethyl groups are particularly preferred.

[0026] Q in equation (24) 1 In terms of the electrical and mechanical properties of the formed resin film, -C6H4-C6H4-, -O-C6H4-C6H4-O-, -O-C6H4-CO-C6H4-O-, -O-C6H4-C(CH3)2-C6H4-O-, -OCO-C6H4-COO-, -OCO-C6H4-C6H4-COO-, -OCO-, -O-, -CO-, -C(CF3)2-, -C(CH3)2-, -CH2-, -O-C6H4-SO2-C6H4-O-, -C(CH3)2-C6H4-C(CH3)2-, -OC 10 H6-O-, -O-C6H4-O-, -O-CH2-O-, -O-(CH2)2-O-, -O-(CH2)3-O-, -O-(CH2)4-O-, -O-(CH2)5-O-, and -O-(CH2)6-O- are preferred. From the viewpoint of improving the electrical and mechanical properties of the formed resin film, Q in formula (24) is preferred. 1 As such, -O-C6H4-C6H4-O- and -O-C6H4-C(CH3)2-C6H4-O- are more preferred, and groups represented as -O-C6H4-C6H4-O- where both -C6H4- are p-phenylene groups are particularly preferred.

[0027] When using an aromatic diamine compound as the diamine compound represented by formula (A2), for example, the aromatic diamine compounds shown below can be suitably used. In other words, aromatic diamine compounds include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 9,10-diaminoanthracene, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4'-diamino Nobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl Phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl Nyl ether, 3-sulfo-4,4'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-Bis(4-aminophenoxy)pentane, 1,6-Bis(4-aminophenoxy)hexane, Bis(3-amino-4-hydroxyphenyl) ether, Bis[4-(4-aminophenoxy)phenyl] ether, Bis[4-(3-aminophenoxy)phenyl] ether, 4,4'-Bis(4-aminophenoxy)biphenyl, 3,4'-Bis(4-aminophenoxy)biphenyl, 3,3'-Bis(4-aminophenoxy)biphenyl, Bis(3-amino-4-hydroxyphenyl)sulfone, Bis(4-aminophen (Noxyphenyl) sulfone, bis(3-aminophenoxyphenyl) sulfone, bis[4-(4-aminophenoxy)phenyl] sulfone, bis[4-(3-aminophenoxy)phenyl] sulfone, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl] sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl] sulfone, bis[4-(4-aminophenoxy)phenyl] ketone, 2,2-bis[4-{4-amino-2-(trifluoromethyl)phenoxy}phenyl [nyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 2,7-diaminofluorene, 2-(4-aminophenyl)-5-aminobenzoxazole, 2- (3-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-6-aminobenzoxazole, 2-(3-aminophenyl)-6-aminobenzoxazole, 1,4-bis(5-amino-2-benzoxazolyl)benzene, 1,4-bis(6-amino-2-benzoxazolyl)benzene, 1,3-bis(5-amino-2-benzoxazolyl)benzene, 1,3-bis(6-amino-2-benzoxazolyl)benzene, 2,6-bis(4-aminophenyl)benzobisoxazole, 2,6-Bis(3-aminophenyl)benzobisoxazole, bis[(3-aminophenyl)-5-benzoxazol], bis[(4-aminophenyl)-5-benzoxazol], bis[(3-aminophenyl)-6-benzoxazol], bis[(4-aminophenyl)-6-benzoxazol], N,N'-bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl) Examples include nobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-[1,4-phenylenebis(1-methylethane-1,1-diyl)]dianiline, 3,5-diamibenzoic acid, 3,4-diaminobenzoic acid, 4-aminobenzoic acid 4-aminophenyl ester, 1,3-bis(4-anilino)tetramethyldisiloxane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, and ortho-tolidine sulfone. Among these, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl, and 3,3'-bis(4-aminophenoxy)biphenyl are preferred in terms of improving electrical and mechanical properties.

[0028] Also, Y A1 As such, silicon atom-containing groups that may have a chain-like aliphatic group and / or an aromatic ring can be employed. Typical silicon atom-containing groups that can be used are those shown below. [ka]

[0029] Specific examples of compounds having amino groups at both ends and silicon atom-containing groups include methylphenyl silicones with amino groups at both ends (for example, X-22-1660B-3 (number average molecular weight approximately 4,400) and X-22-9409 (number average molecular weight approximately 1,300) from Shin-Etsu Chemical Co., Ltd.), and dimethyl silicones with amino groups at both ends (for example, X-22-161A (number average molecular weight approximately 1,600), X-22-161B (number average molecular weight approximately 3,000), and KF8012 (number average molecular weight approximately 4,400) from Shin-Etsu Chemical Co., Ltd.; BY16-835U from Toray Dow Corning (number average molecular weight approximately 900); and Cyraplane FM3311 from JNC Corporation (number average molecular weight approximately 1,000)).

[0030] Furthermore, diamines having an oxyalkylene group can also be preferably used as the diamine compound represented by formula (A2). Preferred examples of the oxyalkylene group include ethylene oxy group and propylene oxy group (-C(CH3)-CH2-O-, -CH2-C(CH3)-O-, or -CH2CH2CH2-O-). A diamine having an oxyalkylene group may contain a combination of two or more oxyalkylene groups. When a diamine having an oxyalkylene group contains two or more oxyalkylene groups, the two or more oxyalkylene groups may be contained in the diamine in a block-like manner or randomly. Diamines having an oxyalkylene group are preferably free of cyclic groups, and more preferably free of aromatic groups. Specific examples of diamines having an oxyalkylene group include, respectively, Jeffermin® KH-511, Jeffermin® ED-600, Jeffermin® ED-900, Jeffermin® ED-2003, Jeffermin® EDR-148, Jeffermin® EDR-176, Jeffermin® D-200, Jeffermin® D-400, Jeffermin® D-2000, and Jeffermin® D-4000, as well as 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, all manufactured by HUNTSUMAN.

[0031] Since it is easy to obtain a polyamide resin that can form a polyimide resin with excellent dielectric properties in the high-frequency band, it is preferable that the diamine compound contains one or more selected from the group consisting of a diamine compound (A-1) represented by the following formula (A1), a diamine compound (A-2) having a substructure represented by the formula (2) described later and not corresponding to diamine compound (A-1), a diamine compound (A-3) having a substructure represented by the formula (A3) described later and not corresponding to diamine compound (A-1) or diamine compound (A-2), and a dimer amine compound (A4).

[0032] (Diamine compound (A-1)) The diamine compound (A-1) is a compound represented by the following formula (A1). [ka] (In formula (A1), X is a tetravalent organic group, and R a1 R is a hydroxyl group, a carboxyl group, or a halogen atom. a2 is an aliphatic group, hydroxyl group, carboxyl group, sulfonic acid group, or halogen atom having 1 to 20 carbon atoms, and Ar is R a2 A phenyl group which may be substituted with, or R a2The naphthyl group may be substituted with a , where ma1 is an integer between 0 and 10, ma2 is an integer between 0 and 7, and ma3 is an integer between 1 and 10. The upper limit of the number of carbon atoms in the diamine compound (A-1) represented by formula (A1) is 40.

[0033] In equation (A1), Ar is R a2 A phenyl group which may be substituted with, or R a2 It is a naphthyl group which may be substituted with . Ar is preferably a phenyl group or a naphthyl group. In other words, in formula (A1), ma2 is preferably 0.

[0034] In equation (A1), R a2 R is an aliphatic group, hydroxyl group, carboxyl group, sulfonic acid group, or halogen atom having 1 to 20 carbon atoms. a2 The organic group may include heteroatoms such as O, N, S, P, B, Si, and halogen atoms. R a2 The number of carbon atoms in the aliphatic group is preferably 1 to 12, and more preferably 1 to 6.

[0035] R a2Aliphatic groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and Chain-like alkyl groups such as n-icosyl group; chain-like alkenyl groups such as vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group Halogenated linear alkyl groups such as perfluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and perfluorodecyl group; halogenated cycloalkyl groups such as 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group, and 4-bromocyclohexyl group; hydroxylinear alkyl groups such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group; hydroxycycloalkyl groups such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group;Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonyloxy group Chain-like alkoxy groups such as decyloxy groups and n-icosyloxy groups; chain-like alkenyloxy groups such as vinyloxy groups, 1-propenyloxy groups, 2-n-propenyloxy groups (allyloxy groups), 1-n-butenyloxy groups, 2-n-butenyloxy groups, and 3-n-butenyloxy groups; methoxymethyl groups, ethoxymethyl groups, n-propoxymethyl groups, 2-methoxyethyl groups, 2-ethoxyethyl groups, 2-n-propoxyethyl groups, 3-methoxy-n-propyl groups, 3-ethoxy-n-propyl groups, 3-n-propoxy-n-propyl groups, 4-methoxymethyl groups Alkoxyalkyl groups such as xy-n-butyl group, 4-ethoxy-n-butyl group, and 4-n-propoxy-n-butyl group; Alkoxyalkoxy groups such as methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n-propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propoxy-n-butyloxy group Aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanol group, octanoyl group, nonanoyl group, and decanoyl group; linear alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyloxycarbonyl group;These are aliphatic acyloxy groups such as formyloxy, acetyloxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanyloxy, octanoyloxy, nonanoyloxy, and decanoyloxy.

[0036] In formula (A1), ma3 is an integer between 1 and 10. The value of ma3 is not particularly limited as long as it is between 1 and 10, and can be appropriately selected depending on the structure of X. The value of ma3 is preferably between 1 and 4, and more preferably 1 or 2.

[0037] In formula (A1), the organic group X may include heteroatoms such as O, N, S, P, B, Si, and halogen atoms. In the compound represented by formula (A1), the two amino groups are each bonded to carbon atoms in the organic group X.

[0038] The organic group X may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. The organic group X may be a group bonded via a bond containing heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of heteroatom-containing bonds in the organic group X that include an oxygen atom, a sulfur atom, and a nitrogen atom include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, with -O-, -CO-, and -S- being preferred.

[0039] If the organic group X is an aliphatic group, it may be either a saturated or unsaturated aliphatic group. If the organic group X is an aliphatic group, it is preferable that it is an aliphatic hydrocarbon group. If the organic group X is an aliphatic group, it may be linear, cyclic, or a combination of a linear aliphatic group and a cyclic aliphatic group. The linear aliphatic group may be branched.

[0040] When the organic group X is an aliphatic group, the aliphatic group is preferably an alkylene group having 1 to 20 carbon atoms from which (ma1+ma3+2) hydrogen atoms have been removed, more preferably an alkylene group having 1 to 16 carbon atoms from which (ma1+ma3+2) hydrogen atoms have been removed, and even more preferably an alkylene group having 1 to 12 carbon atoms from which (ma1+ma3+2) hydrogen atoms have been removed.

[0041] If the organic group X is a group containing an aromatic group, then X, Ar, and R in formula (A1) a1 , and R a2 Examples of groups composed of these are those represented by the following equations (11) to (15). [ka]

[0042] In equations (11) to (15), Ar, R a1 , R a2 ma1, ma2, and ma3 are the same as those in equation (A1). In equation (13), ma4 and ma5 are each independent integers between 0 and 4. ma6 and ma7 are each independent integers between 0 and 4, and the sum of ma6 and ma7 is between 1 and 8. In equation (14), ma8, ma9, and ma10 are each independent integers between 0 and 4. The sum of ma8, ma9, and ma10 is between 0 and 10. ma11, ma12, and ma13 are each independent integers between 0 and 4. The sum of ma11, ma12, and ma13 is between 1 and 10. In equation (15), ma14 is an integer between 0 and 3. ma15 is an integer between 0 and 5. The sum of ma14 and ma15 is between 0 and 8. ma16 is an integer between 0 and 3. ma17 is an integer between 0 and 5 (inclusive). The sum of ma16 and ma17 is between 1 and 8 (inclusive).

[0043] In formula (11), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2. In formula (12), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2. In formula (13), ma2 is preferably 0, ma4 and ma5 are each preferably 0, ma6 and ma7 are each preferably 0, 1, or 2, and the sum of ma6 and ma7 is 1 or more, and preferably 4 or less. In formula (14), ma2 is preferably 0, ma8, ma9, and ma10 are each preferably 0, ma11, ma12, and ma13 are each preferably 0, 1, or 2, and the sum of ma11, ma12, and ma13 is 1 or more, and preferably 6 or less. In formula (15), ma2 is preferably 0, ma14 and ma15 are each preferably 0, ma16 and ma17 are each preferably 0, 1, or 2, and the sum of ma16 and ma17 is 1 or more and preferably 4 or less.

[0044] In equations (11) to (15), R a3The linking group is a single bond or a divalent linking group. However, the divalent linking group is not a group containing an aromatic group. Examples of divalent linking groups include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, as well as groups formed by combining two or more of these groups. The number of carbon atoms in the linking group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. The aliphatic hydrocarbon group as a linking group may have one or more unsaturated bonds, may be branched, and may contain a ring structure. Specific examples of aliphatic hydrocarbon groups used as linking groups include methylene group, ethane-1,2-diyl group (ethylene group), ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, and undecane-1,1 Examples include 1-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, icosane-1,20-diyl group, ethene-1,2-diyl group (vinylene group), propene-1,3-diyl group, ethyne-1,2-diyl group, and propyne-1,3-diyl group.

[0045] Preferred examples of linking groups include alkylene groups having 1 to 6 carbon atoms, alkenylene groups having 2 to 6 carbon atoms, alkylene groups having 2 to 6 carbon atoms, alkylene oxy groups having 1 to 6 carbon atoms, alkenylene oxy groups having 2 to 6 carbon atoms, alkylene oxy groups having 2 to 6 carbon atoms, alkylentione groups having 1 to 6 carbon atoms, alkenylene oxy groups having 2 to 6 carbon atoms, alkylene amino groups having 1 to 6 carbon atoms, alkenylene amino groups having 2 to 6 carbon atoms, alkylene amino groups having 2 to 6 carbon atoms, -CONH-, -NH-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, -OCONH-, and -OCOO-.

[0046] The resulting resin film exhibits a low dielectric loss tangent and good mechanical properties, and the diamine compound (A-1) represented by formula (A1) is as follows: [ka] (In formula (A1-1), R a1 , R a2 Ar, ma1, ma2, and ma3 are the same as those in equation (A1), and Y a1 This is an organic group having 1 to 20 carbon atoms, or a single bond, Y a2 (This refers to an organic group with 1 to 20 carbon atoms, where na1 is either 0 or 1, and na2 is either 0 or 1. If na1 is 1, Ya1 is not a single bond.) It is preferable that the compound is represented by [formula].

[0047] In formula (A1-1), Y a1 The organic group may include heteroatoms such as O, N, S, P, B, Si, and halogen atoms. a1 The organic group is preferably a hydrocarbon group. a1 The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. a1As the hydrocarbon group, an aromatic hydrocarbon group is preferred, and a phenylene group and a naphthalene diyl group are more preferred. a1 Suitable examples of aromatic hydrocarbon groups include p-phenylene, m-phenylene, o-phenylene, naphthalene-1,4-diyl, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, and naphthalene-2,3-diyl. Among these aromatic hydrocarbon groups, p-phenylene and m-phenylene are preferred, with p-phenylene being more preferred.

[0048] In formula (A1-1), it is preferable that na2 is 1, and both na1 and na2 are 1, Y a1 It is more preferable that the group is an organic group. In this case, due to the high steric degree of freedom of the ether bond, when forming a cured film using the photosensitive resin composition, the constituent unit represented by formula (A1-1) is easily packed, and it is thought that a cured film with excellent mechanical properties, thermal properties, electrical properties, etc., can be easily formed.

[0049] In formula (A1-1), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.

[0050] The following compounds are specific examples of the diamine compound (A-1) represented by formula (A1) described above. [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] (Diamine compound (A-2)) Diamine compound (A-2) is a diamine compound that has a substructure represented by the following formula (A2) and does not fall under the category of diamine compound (A-1). [ka] (In formula (A2), R a3 and R a4 Each of these is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and ma4 and ma5 are independently integers between 0 and 4.

[0059] In formula (A2), R a3 and R a4Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. Among these alkyl groups, methyl and ethyl groups are preferred, with methyl being more preferred. In formula (A2), R a3 and R a4 Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy groups. Among these alkoxy groups, methoxy and ethoxy groups are preferred, with methoxy groups being more preferred. In formula (A2), R a3 and R a4 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Among these halogen atoms, chlorine and bromine are preferred.

[0060] In formula (A2), ma4 and ma5 are each an independent integer between 0 and 4. Because the diamine compound (A-2) is readily available, ma4 and ma5 are preferably integers between 0 and 2, and more preferably 0.

[0061] Suitable compounds for the diamine compound (A2) include those represented by the following formula (A2-1). [ka] (In formula (A2-1), X 1 and X 2 Each of these is an aromatic hydrocarbon group that may be independently substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and halogen atoms. a3 , R a4ma4 and ma5 are the same as those in formula (A2). However, the upper limit of the number of carbon atoms in the diamine compound (A2) represented by formula (A2-1) is 40.

[0062] X in equation (A2-1) 1 and X 2 Each of these is a divalent aromatic hydrocarbon group that may be independently substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and halogen atoms. Examples of alkyl groups having 1 to 4 carbon atoms as substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. Among these alkyl groups, methyl and ethyl groups are preferred, with methyl groups being more preferred. Examples of alkoxy groups having 1 to 4 carbon atoms as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy groups. Among these alkoxy groups, methoxy and ethoxy groups are preferred, with methoxy groups being more preferred. Examples of halogen atoms used as substituents include fluorine, chlorine, bromine, and iodine. Among these halogen atoms, chlorine and bromine are preferred.

[0063] X 1 and X 2 The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited as long as the number of carbon atoms in the diamine compound represented by formula (A2-1) is 40 or less. For example, 6 to 50 is preferred, and 6 to 20 is more preferred. Note that the number of carbon atoms in the aromatic hydrocarbon group mentioned above does not include the number of carbon atoms in the substituents. X 1 , and X 2Preferred aromatic hydrocarbon groups include phenylene groups such as o-phenylene, m-phenylene, and p-phenylene groups; naphthalenediyl groups such as naphthalene-1,4-diyl, naphthalene-1,3-diyl, naphthalene-2,6-diyl, and naphthalene-2,7-diyl groups; and biphenyldiyl groups such as biphenyl-4,4'-diyl, biphenyl-3,4'-diyl, and biphenyl-3,3'-diyl groups.

[0064] X 1 , and X 2 The preferred groups are p-phenylene, m-phenylene, naphthalene-1,4-diyl, and biphenyl-4,4'-diyl, more preferably p-phenylene and biphenyl-4,4'-diyl, and even more preferably p-phenylene.

[0065] The following compounds are specific examples of the diamine compound (A-2) represented by formula (A2) described above. [ka]

[0066] (Diamine compound (A-3)) Diamine compound (A-3) has a substructure represented by the following formula (A3) and is a diamine compound that does not fall under diamine compound (A-1) or diamine compound (A-2). [ka] (In formula (A3), R a5 and R a6 Each is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and ma6 and ma7 are independently integers between 0 and 4, R a7 and R a8 Each of these is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R a7 and R a8They may be combined with each other to form a ring.)

[0067] In formula (A3), R a5 and R a6 Examples of the alkyl group having 1 to 4 carbon atoms as R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.) In formula (A3), R a5 and R a6 Examples of the alkoxy group having 1 to 4 carbon atoms as R include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.) In formula (A3), R[[ID=1​​​​​​​​​​​​​​​​​​​​Examples of the alkyl halide group having 1 to 4 carbon atoms include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, and 1,1,2,2,2-pentafluoroethyl group. R in formula (A3) a7 and R a8 are preferably a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, and a phenyl group, because of good solubility of the polyamide resin in an organic solvent and easy availability of the diamine compound (A-3). Also, it is also preferable that R a7 and R a8 are bonded to each other to form a cycloalkylidene group having 5 to 8 carbon atoms such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, and a cyclooctylidene group.

[0070] Preferable specific examples of the partial structure represented by formula (A3) include the following structures.

Chemical formula

[0071] Preferable compounds as the diamine compound (A-3) include the compounds represented by the following formula (A3-1).

Chemical formula

[0072] X in equation (A3-1) 3 and X 4 Each of these is a divalent aromatic hydrocarbon group that may be independently substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and halogen atoms. Examples of alkyl groups having 1 to 4 carbon atoms as substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. Among these alkyl groups, methyl and ethyl groups are preferred, with methyl groups being more preferred. Examples of alkoxy groups having 1 to 4 carbon atoms as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy groups. Among these alkoxy groups, methoxy and ethoxy groups are preferred, with methoxy groups being more preferred. Examples of halogen atoms used as substituents include fluorine, chlorine, bromine, and iodine. Among these halogen atoms, chlorine and bromine are preferred.

[0073] X 3 and X 4 The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited as long as the number of carbon atoms in the diamine compound represented by formula (A3-1) is 40 or less. Note that the number of carbon atoms in the aromatic hydrocarbon group mentioned above does not include the number of carbon atoms in the substituents. X 3 and X 4 Preferred aromatic hydrocarbon groups include phenylene groups such as o-phenylene, m-phenylene, and p-phenylene groups; naphthalenediyl groups such as naphthalene-1,4-diyl, naphthalene-1,3-diyl, naphthalene-2,6-diyl, and naphthalene-2,7-diyl groups; and biphenyldiyl groups such as biphenyl-4,4'-diyl, biphenyl-3,4'-diyl, and biphenyl-3,3'-diyl groups.

[0074] X 3 and X 4 The preferred groups are p-phenylene, m-phenylene, naphthalene-1,4-diyl, and biphenyl-4,4'-diyl, more preferably p-phenylene and biphenyl-4,4'-diyl, and even more preferably p-phenylene.

[0075] The following compounds are specific examples of the diamine compound (A-3) represented by formula (A3) described above. [ka]

[0076] [ka]

[0077] (Dimer amine compound (A-4)) Dimer amine compound (A-4) is also preferred as a diamine compound because it is easy to form cured products with low dielectric constant and dielectric loss tangent in the high-frequency band using a photosensitive resin composition. Dimer amine compound (A-4) is a diamine compound obtained in which the two terminal carboxyl groups of a dimer acid are replaced with aminomethyl groups or amino groups. Dimer acid is a known dibasic acid obtained by the intermolecular polymerization reaction of unsaturated fatty acids. Industrial manufacturing processes for producing dimer acid are almost standardized. Typically, dimer acid is obtained by dimerizing an unsaturated fatty acid having 11 to 22 carbon atoms in the presence of a clay catalyst or the like. However, the upper limit of the number of carbon atoms for dimer amine compound (A-4) is 40. Industrially obtained dimer acid is mainly composed of dibasic acids with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms, such as oleic acid, linoleic acid, and linolenic acid. Industrially obtained dimer acids may contain arbitrary amounts of monomeric acids with 18 carbon atoms, trimer acids with 54 carbon atoms, and other polymeric fatty acids with 20 to 54 carbon atoms, depending on the degree of purification. As the dimer amine compound (A-4), a diamine compound represented by the following formula (31) is preferred. [ka]

[0078] In equation (31), e, f, g, and h are each integers greater than or equal to 0. e + f is an integer between 6 and 17, and g + h is an integer between 8 and 19. In equation (31), the dashed part represents a carbon-carbon single bond or a carbon-carbon double bond. However, there is at least one carbon-carbon double bond in one molecule of the compound represented by equation (31).

[0079] Furthermore, since it is possible to form a cured product with superior elongation, the compound represented by formula (32) below is preferred as the diamine compound represented by formula (31). [ka]

[0080] Commercially available diamine compounds represented by formula (31) include Versamin 551 (manufactured by BASF) and Priamine 1074 (manufactured by Croda Japan), which contain the compound represented by formula (33) below, and Versamin 552 (manufactured by BASF), Priamine 1073 (manufactured by Croda Japan), and Priamine 1075 (manufactured by Croda Japan), which contain the compound represented by formula (32) above. Such commercially available dimer amine compounds (A-4) are usually mixtures containing multiple amine compounds. [ka]

[0081] Furthermore, by reacting the diamine compound represented by formula (31) with an acid halide derived from trimellitic anhydride, a tetracarboxylic dianhydride represented by the following formula (34) can be obtained. It is also preferable to use the tetracarboxylic dianhydride represented by the following formula (34) as a raw material for producing polyimide resin (Al) and polyamic acid (A-II). In equation (34), i, j, k, and l are each integers greater than or equal to 0. i+j is an integer between 6 and 17, and k+l is an integer between 8 and 19. In equation (34), the dashed part represents a carbon-carbon single bond or a carbon-carbon double bond. [ka]

[0082] The ratio of the number of moles of one or more compounds selected from the group consisting of diamine compound (A-1), diamine compound (A-2), diamine compound (A-3), and dimeramine compound (A-4) to the total number of moles of diamine compounds is preferably 10 mol% or more and 100 mol% or less, more preferably 15 mol% or more and 100 mol% or less, and even more preferably 20 mol% or more and 100 mol% or less.

[0083] <Dicarboxylic acid> As the dicarboxylic acid, we use a dicarboxylic acid that is a reaction product of a tetracarboxylic dianhydride and an alcohol. In the above formula (1), R A1 , and R A2 However, as can be seen from the fact that it is an organic group with 3 to 20 carbon atoms, alcohols have 3 to 20 carbon atoms.

[0084] As for the alcohols, alcohols having radical polymerizable groups are preferred. When using alcohols having radical polymerizable groups, the dicarboxylic acid has radical polymerizable groups. By using a dicarboxylic acid having radical polymerizable groups, a polyamide resin having radical polymerizable groups can be obtained. As radical polymerizable groups, carbon-carbon unsaturated double bond-containing groups are preferred. Preferred specific examples of carbon-carbon unsaturated double bond-containing groups include vinyl groups, alkenyl groups such as allyl groups, and (meth)acrylic group-containing groups.

[0085] A polyamide resin film patterned to a desired shape can be obtained by photolithography using a photosensitive varnish containing a photopolymerization initiator along with a polyamide resin having radical polymerizable groups. Furthermore, a patterned polyimide resin film can be obtained by imidizing the patterned polyamide resin film by methods such as heating. Hereinafter, the reaction product of tetracarboxylic dianhydride and alcohols having radical polymerizable groups will also be referred to as "polymerizable dicarboxylic acid."

[0086] When the polyamide resin obtained by polycondensation of the above polymerizable dicarboxylic acid with a diamine compound is heated, imidization occurs through ring closure accompanied by the elimination of organic groups derived from alcohols, resulting in the formation of a polyimide resin.

[0087] The ratio of the number of moles of polymerizable dicarboxylic acid to the total number of moles of dicarboxylic acid is preferably 10 mol% to 100 mol%, more preferably 30 mol% to 100 mol%, even more preferably 50 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, and particularly preferably 100 mol%.

[0088] [Dicarboxylic acid] As mentioned above, dicarboxylic acids are reaction products of tetracarboxylic dianhydrides and alcohols.

[0089] (Tetracarboxylic acid dianhydride) The tetracarboxylic dianhydride is not particularly limited as long as the desired effect is not impaired. Typically, tetracarboxylic dianhydrides that have been conventionally used in the production of polyamic acids and polyimide resins can be preferably used. Examples of tetracarboxylic dianhydrides include compounds represented by the following formula (A3). Tetracarboxylic dianhydrides may be used individually or in combination of two or more types. [ka] (In formula (A3), X A1 (This refers to a tetravalent organic group with 6 to 50 carbon atoms.)

[0090] In formula (A3), X A1 This is a tetravalent organic group having 6 to 50 carbon atoms, and may have one or more substituents in addition to the two -CO-O-CO- acid anhydride groups represented by formula (A3). Preferred examples of substituents include fluorine atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, fluorinated alkyl groups having 1 to 6 carbon atoms, and fluorinated alkoxy groups having 1 to 6 carbon atoms. In addition, the compound represented by formula (a1-1) may contain a carboxyl group or a carboxylic acid ester group in addition to the acid anhydride group. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferable that it be a perfluoroalkyl group or a perfluoroalkoxy group. The same applies to the substituents described above, as well as to the one or more substituents that the aromatic group may have on its aromatic ring, as described later.

[0091] X A1 The number of carbon atoms constituting the compound is more preferably 8 or more, and even more preferably 12 or more. Also, X A1 The number of carbon atoms constituting the compound is more preferably 40 or less, and even more preferably 30 or less. A1 This group may be an aliphatic group, an aromatic group, or a combination of these structures. A1 In addition to carbon atoms and hydrogen atoms, it may also contain halogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. A1If it contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, nitrogen atom, or sulfur atom is a group selected from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, X A1 It may be included as a group selected from -O-, -CO-, -S-, and X A1 It is preferable to give birth to them.

[0092] The tetracarboxylic dianhydride represented by formula (A3) may be an aliphatic tetracarboxylic dianhydride having two dicarboxylic anhydride groups bonded to an aliphatic group, or an aromatic tetracarboxylic dianhydride having at least one dicarboxylic anhydride group bonded to an aromatic group. Furthermore, it is preferable that the aromatic tetracarboxylic dianhydride has two dicarboxylic anhydride groups bonded to the aromatic group.

[0093] Aliphatic tetracarboxylic dianhydrides may contain an alicyclic structure. The alicyclic structure may be polycyclic. An example of an aliphatic tetracarboxylic dianhydride that does not have an alicyclic structure is 1,2,3,4-tetracarboxylic dianhydride (e.g., Ricacid BT-100, manufactured by Shin Nippon Rika Co., Ltd.). Aliphatic tetracarboxylic dianhydrides having an alicyclic structure include cyclobutanetetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride (e.g., Enehyde® CpODA, manufactured by ENEOS Corporation), 2,2-bis(2, Examples include 3-dicarboxyphenoxy)hexafluoropropane dianhydride [5,5'-(1,4-phenylene)bisnorbornane]-2,2',3,3'-tetracarboxylic dianhydride (e.g., Enehyde® BzDA, manufactured by ENEOS Corporation) and 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (e.g., Ricacid TDA-100, manufactured by Shin Nippon Rika Co., Ltd.).

[0094] Examples of aromatic tetracarboxylic dianhydrides represented by formula (A3) and having two dicarboxylic acid anhydride groups bonded to an aromatic group include pyromellitic acid dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 4,4'-oxydiphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic acid dianhydride, trimellitic acid (3,4-dicarboxyphenyl) dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, and 2,3,6,7-naphthalenetetra Examples include carboxylic acid dianhydrides, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, bis(2,3-dicarboxyphenoxy)methane dianhydride, 1,1-bis(2,3-dicarboxyphenoxy)ethane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., Ricacid TMEG100, manufactured by Shin Nippon Rika Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Kasei Co., Ltd.). Among these aromatic tetracarboxylic dianhydrides, 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 4,4'-bis(3,4-dicarboxyphenyloxy)biphenyl dianhydride, 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, and α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride are preferred because they readily form cured products with excellent electrical properties. The number of carbon atoms in the linear alkylene group in α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride is preferably 1 to 20, and more preferably 2 to 12. Suitable specific examples of α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydrides include 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., Ricacid TMEG100, manufactured by Shin Nippon Rika Co., Ltd.) and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Kasei Co., Ltd.).

[0095] Furthermore, it is preferable that the aromatic tetracarboxylic dianhydride is biphenyltetracarboxylic dianhydride, as this suppresses warping of the cured film of the photosensitive resin composition and provides good photolithography properties for the photosensitive resin composition. Examples of biphenyltetracarboxylic dianhydrides include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyltetracarboxylic dianhydride, with 3,3',4,4'-biphenyltetracarboxylic dianhydride being preferred.

[0096] The aromatic tetracarboxylic dianhydride may also be, for example, a compound represented by the following general formulas (a3-2) to (a3-4). [ka]

[0097] In the above equations (a3-2) and (a3-3), R a01 , R a02 and R a03 Each of these represents a divalent group consisting of an aliphatic group which may be substituted with a halogen, an oxygen atom, a sulfur atom, an aromatic group via one or more divalent elements, or a combination thereof. a02 and R a03 They may be the same or different. That is, R a01 , R a02 and R a03 This may include a carbon-carbon single bond, a carbon-oxygen-carbon ether bond, or a halogen element (fluorine, chlorine, bromine, iodine). Examples of compounds represented by formula (a3-2) include 2,2-bis(3,4-dicarboxyphenoxy)propane dianhydride, bis(3,4-dicarboxyphenoxy)methane dianhydride, 1,1-bis(3,4-dicarboxyphenoxy)ethane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene, 2,2-bis(3,4-dicarboxyphenoxy)hexafluoropropane dianhydride, and 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride.

[0098] Furthermore, in the above formula (a3-4), R a04 , R a05 R represents a monovalent substituent consisting of an aliphatic group which may be substituted with a halogen, an aromatic group via one or more divalent elements, a halogen, or a combination thereof. a04 , and R a05 These may be the same or different. As the compound represented by formula (a3-4), difluoropyromellitic dianhydride and dichloropyromellitic dianhydride can also be used.

[0099] Polyamide resins produced using polymerizable dicarboxylic acids have radical polymerizable groups on their molecular chains. Therefore, the tetravalent organic group X in formula (A3) A1The base may be represented by the following formulas (a3-5) to (a3-7). [ka] In equations (a3-5) to (a3-7), R a01 , R a02 , and R a03 In the aforementioned equations (a3-2), (a3-3), and (a3-4), R a01 , R a02 , and R a03 It is similar to that. In equations (a3-5), (a3-6), and (a3-7), R a06 This is a radical polymerizable group. Radical polymerizable groups will be discussed later.

[0100] (Alcoholic beverages) As mentioned above, it is preferable that the alcohols include alcohols having 3 to 20 carbon atoms and a carbon-carbon double bond. Therefore, alcohols with a carbon-carbon double bond and a number of carbon atoms between 3 and 20 are used, either partially or entirely.

[0101] Hereafter, alcohols with 3 to 20 carbon atoms containing a carbon-carbon double bond will be referred to as Alcohol I. All other alcohols will be referred to as Alcohol II. The alcohols preferably contain alcohol I, but they may consist only of alcohol II.

[0102] Alcohol I The dicarboxylic acid has two carboxylic acid ester groups formed by the reaction of a carboxylic acid anhydride group with the above-mentioned alcohols. In terms of the photopolymerizability of the resulting polyimide resin, the ratio of the number of moles of carboxylic acid ester groups derived from alcohol I to the total number of moles of the aforementioned carboxylic acid ester groups in the dicarboxylic acid is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more.

[0103] As for alcohol I, the following alcohol I-1 is preferred because it has a low dielectric loss tangent and readily forms polyimide resins with excellent chemical resistance. Furthermore, alcohol I may also include alcohol I-2, which is not one of the alcohols listed below. Alcohol I-1 is an alcohol that has a secondary hydroxyl group in combination with an ethylenically unsaturated double bond, or a methylol group in combination with an ethylenically unsaturated double bond.

[0104] In the claims of this application, a methylol group is defined as a hydroxymethyl group bonded to a secondary carbon atom, a tertiary carbon atom, a carbon atom bonded to one carbon atom and one heteroatom, a carbon atom bonded to two heteroatoms, or a carbon atom in an aromatic ring. For example, a hydroxyethyl group consists of a hydroxymethyl group and a methylene group. However, according to the above definition, in the specification and claims of this application, the hydroxymethyl group bonded to the primary carbon atom in the methylene group, which is included in the hydroxyethyl group, does not fall under the category of a methylol group.

[0105] When producing alcohol I-1, a mixture containing alcohol I-2 may inevitably be produced along with alcohol I-1 due to the manufacturing method. For example, when producing alcohol I by reacting a polyol having a secondary hydroxyl group or a methylol group and a primary hydroxyl group with (meth)acrylate halide or allyl halide, alcohols having (meth)acryloyl or allyl groups along with the primary hydroxyl group may be produced as by-products. A mixture containing alcohol I-2 along with alcohol I-1 produced by this method can be used as the alcohols to react with tetracarboxylic dianhydride. The ratio of the number of moles of alcohol I-1 to the total number of moles of alcohol I-II is not particularly limited. The ratio of the number of moles of alcohol I-1 to the total number of moles of alcohol I-II is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol%, and particularly preferably 100 mol%.

[0106] As described above, alcohol I has an ethylenically unsaturated double bond. Typically, the ethylenically unsaturated double bond-containing group is preferably an alkenyl group-containing group, including vinyl groups and allyl groups, and more preferably an (meth)acryloyl group-containing group. As mentioned above, dicarboxylic acids contain residues with ethylenically unsaturated double bonds derived from alcohol I. Therefore, polyamide resins also contain residues with ethylenically unsaturated double bonds derived from alcohol I.

[0107] Alcohol I-1 Alcohol I-1 is an alcohol that has a secondary hydroxyl group in combination with an ethylenically unsaturated double bond, or a methylol group in combination with an ethylenically unsaturated double bond. Alcohol I-1 may have two or more hydroxyl groups in combination. Alcohol I-1 may have a secondary hydroxyl group and a methylol group in combination. Alcohol I-1 preferably has one secondary hydroxyl group or one methylol group.

[0108] When alcohol I-1 has two or more ethylenically unsaturated double bonds, alcohol I is preferably a (meth)acrylate such as glycerin, trimethylolpropane, pentaerythritol, or dipentaerythritol. Suitable examples of alcohol I-1 having two or more ethylenically unsaturated double bonds include glycerin-1,3-di(meth)acrylate, glycerin-1,2-di(meth)acrylate, trimethylolpropanedi(meth)acrylate, pentaerythritoltri(meth)acrylate, and dipentaerythritolpenta(meth)acrylate. These compounds may have a combination of acryloyl and methacryloyl groups.

[0109] When alcohol I-1 has one ethylenically unsaturated double bond, alcohol I is preferably at least one selected from the compounds represented by the following formula (I) and the compounds represented by the following formula (II). CH=CR 1 -CO-OR 2 -CHR 3 -OH (I) CH=CR 1 -CO-OR 4 -CH2-OH (II) (In formula (I), R 1 R is a hydrogen atom or a methyl group, 2 It is bonded to the oxygen atom in the ester bond by a CO bond, R 3 It is a divalent organic group that is bonded to a carbon atom by a CC bond, and R 3 R 3 It is a monovalent organic group that is bonded to a carbon atom by a CC bond, and R 2 and R 3 They may combine to form a ring, In formula (II), R 1 R is a hydrogen atom or a methyl group, 4 It is a divalent organic group that is bonded to the oxygen atom in the ester bond via a CO bond and to the methylol group in formula (II) via a CC bond.

[0110] In the above equation (I), R 2 It is bonded to the oxygen atom in the ester bond by a CO bond, R 3It is a divalent organic group bonded to a carbon atom by a CC bond. This divalent organic group may also contain heteroatoms such as halogen atoms, O, S, and N. R in equation (I) 2 The number of carbon atoms in the divalent organic group is not particularly limited, as long as the number of carbon atoms in the alcohol represented by formula (I) is 20 or less. The number of carbon atoms in the divalent organic group is preferably 1 to 12, and more preferably 1 to 8.

[0111] R in equation (I) 2 As the divalent organic group, a divalent hydrocarbon group is preferred. The divalent hydrocarbon group may include a cyclic group. The cyclic group may be an aliphatic ring, an aromatic ring, or a fused ring formed by the fusion of an aliphatic ring and an aromatic ring. 2 As the divalent hydrocarbon group, an alkylene group is preferred.

[0112] Suitable examples of alkylene groups include methylene group, ethane-1,2-diyl group (ethylene group), ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, and octane-1,8-diyl group. Among these, methylene groups, ethane-1,2-diyl groups (ethylene groups), propane-1,3-diyl groups, butane-1,4-diyl groups, and pentane-1,5-diyl groups are preferred.

[0113] In equation (I), R 3 R 3 It is a monovalent organic group bonded to a carbon atom by a CC bond. This monovalent organic group may also contain heteroatoms such as halogen atoms, O, S, and N. R in equation (I) 3The number of carbon atoms in the monovalent organic group is not particularly limited, as long as the number of carbon atoms in the alcohol represented by formula (I) is 20 or less. The number of carbon atoms in the monovalent organic group is preferably 1 to 12, and more preferably 1 to 8.

[0114] R in equation (I) 3 The monovalent organic group may be a linear aliphatic group, a cyclic group, or a group consisting of a linear aliphatic group and a cyclic group. The cyclic group may be an aliphatic ring, an aromatic ring, or a fused ring formed by the fusion of an aliphatic ring and an aromatic ring.

[0115] R in equation (I) 3 Specific examples of monovalent organic groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl; methoxymethyl, ethoxymethyl, n-propyloxymethyl, n-butyloxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propyloxyethyl, 2-n-butyloxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-n-propyloxypropyl, 3-n-butyloxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 4-n-propyloxybutyl, and 4 Examples include alkoxyalkyl groups such as n-butyloxybutyl group; aryloxyalkyl groups such as phenoxymethyl group, 2-phenoxyethyl group, 3-phenoxypropyl group, and 4-phenoxybutyl group; and cycloalkyloxyalkyl groups such as cyclopentyloxymethyl group, 2-cyclopentyloxyethyl group, 3-cyclopentyloxypropyl group, 4-cyclopentyloxybutyl group, cyclohexyloxymethyl group, 2-cyclohexyloxyethyl group, 3-cyclohexyloxypropyl group, 4-cyclohexyloxybutyl group, cycloheptyloxymethyl group, 2-cycloheptyloxyethyl group, 3-cycloheptyloxypropyl group, and 4-cycloheptyloxybutyl group.

[0116] In equation (I), -R 2 -CHR 3 The following are some suitable examples of the divalent group represented by -. In the following examples, * is the terminal bond that connects to the oxygen atom in the ester bond in formula (I). ** is the terminal bond that connects to the hydroxyl group in formula (I). Furthermore, since polyimide resins formed using polyamide resins exhibit a low dielectric loss tangent and excellent chemical resistance, -R in formula (I) 2 -CHR 3 It is preferable that the divalent group represented by - includes a cyclic group. Such a cyclic group may be an aromatic group, an alicyclic group, or a fused cyclic group formed by the fusion of an aromatic ring and an aliphatic ring. [ka]

[0117] Preferred specific examples of compounds represented by formula (I) include the following compounds. [ka]

[0118] In equation (II) above, R 4 This is a divalent organic group that is bonded to the oxygen atom in the ester bond by a CO bond and to the methylol group in formula (II) by a CC bond. This divalent organic group may also contain heteroatoms such as halogen atoms, O, S, and N. R in equation (II) 4 The number of carbon atoms in the divalent organic group is not particularly limited, as long as the number of carbon atoms in the alcohol represented by formula (II) is 20 or less. The number of carbon atoms in the divalent organic group is preferably 1 to 12, and more preferably 1 to 8.

[0119] R in equation (II) 4The divalent organic group as such may be a chain aliphatic group, a cyclic group, or a group composed of a chain aliphatic group and a cyclic group. The cyclic group may be an aliphatic ring, an aromatic ring, or a condensed ring in which an aliphatic ring and an aromatic ring are condensed.

[0120] In formula (II), R 4 Preferable specific examples of the divalent group represented by are as follows. In the following specific examples, * is the end of the bond that binds to the oxygen atom in the ester bond in formula (II). ** is the end of the bond that binds to the methylol group of formula (II).

Chemical formula

[0121] Preferable specific examples of the compound represented by formula (II) include the following compounds.

Chemical formula

[0122] · Alcohol I-2 Alcohol I-2 is an alcohol having 3 to 20 carbon atoms with a carbon-carbon double bond (ethylenically unsaturated double bond) and does not correspond to alcohol I-1. Alcohol I-2 has an ethylenically unsaturated double bond-containing group. As the ethylenically unsaturated double bond-containing group, an alkenyl group-containing group containing an alkenyl group such as a vinyl group and an allyl group is preferable, and a (meth)acryloyl group-containing group is more preferable.

[0123] Preferable examples of the alcohols having an ethylenically unsaturated double bond-containing group as alcohol I-2 include mono (meth)acrylates of diols, N-hydroxyalkyl-substituted (meth)acrylamides, hydroxyl group-containing unsaturated ketones, alkenyl alcohols, and monoalkenyl ethers of diols having an alkenyl group with 3 or more carbon atoms. However, these alcohols do not have a secondary hydroxyl group or a methylol group.

[0124] Examples of diols that provide mono(meth)acrylates of diols include alkanediols (alkylene glycols) such as ethylene glycol, 1,2-propanediol, and 1,3-propanediol; oligo- or polyalkylene glycols such as diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; and cycloalkanediols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 1,2-cyclohexanediol. The diols that provide mono(meth)acrylates of diols are not limited to these. The number of carbon atoms of the alkanediol is preferably 2 or more and 10 or less, more preferably 2 or more and 6 or less, and still more preferably 2 or more and 4 or less. The number of carbon atoms of the oligo- or polyalkylene glycol is preferably 4 or more and 20 or less, and more preferably 4 or more and 10 or less. The number of carbon atoms of the cycloalkanediol is preferably 4 or more and 8 or less, and more preferably 5 or more and 7 or less. The alkanediol and the oligo- or polyalkylene glycol may be linear or branched.

[0125] The number of carbon atoms of the N-hydroxyalkyl group in the N-hydroxyalkyl-substituted (meth)acrylamide is preferably 2 or more and 10 or less, more preferably 2 or more and 6 or less, and even more preferably 2 or more and 4 or less. The N-hydroxyalkyl group in the N-hydroxyalkyl-substituted (meth)acrylamide may be linear or branched. The N-hydroxyalkyl group in the N-hydroxyalkyl-substituted (meth)acrylamide does not have a secondary hydroxyl group or a methylol group.

[0126] The hydroxyl group-containing unsaturated ketone is preferably a compound in which a hydroxyalkyl group and an alkenyl group are bonded to a carbonyl group. The number of carbon atoms in the hydroxyalkyl group is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4. The hydroxyalkyl group may be linear or branched. The hydroxyalkyl group does not have a secondary hydroxyl group or a methylol group. The number of carbon atoms in the alkenyl group is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4. The alkenyl group may be linear or branched.

[0127] The number of carbon atoms in the alkenyl alcohol is preferably 3 to 10, more preferably 3 to 6, and even more preferably 3 or 4. The alkenyl alcohol may be linear or branched. The alkenyl alcohol does not have a secondary hydroxyl group or a methylol group.

[0128] For monoalkenyl ethers of diols having an alkenyl group with 3 or more carbon atoms, the diols that give the monoalkenyl ether are the same as the diols that give the mono(meth)acrylate of the diol. The alkenyl group has 3 or more carbon atoms, preferably 3 to 10, and more preferably 3 to 6. The alkenyl group may be linear or branched.

[0129] Preferred specific examples of alcohol I-2 having a radical polymerizable group include mono(meth)acrylates of diols such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 2-(2-hydroxyethoxy)ethyl (meth)acrylate; N-hydroxyalkyl-substituted (meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide and N-(3-hydroxypropyl)(meth)acrylamide; and hydroxyl-containing ketones such as (hydroxymethyl) vinyl ketone and (2-hydroxyethyl) vinyl ketone.

[0130] • Alcohol II Alcohol II is an alcohol that does not fall under the category of Alcohol I. The structure of Alcohol II is not particularly limited, as long as the desired effect is not impaired.

[0131] Examples of alcohol II include alkane monools such as n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol; phenols or naphthols such as phenol, p-cresol, m-cresol, o-cresol, α-naphthol, and β-naphthol; monoethers of glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, 1,3-propanediol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; and alcohols having radical polymerizable groups that do not fall under alcohol I.

[0132] (Production of dicarboxylic acids) Dicarboxylic acids are obtained by reacting the tetracarboxylic dianhydride described above with alcohols. The alcohols react with the carboxylic acid anhydride group to produce a carboxyl group and an ester group.

[0133] In the aforementioned tetracarboxylic dianhydride, R a21 Dicarboxylic acids can be obtained by reacting alcohols represented by -OH. R a21 These are residues obtained by removing the hydroxyl group from the aforementioned alcohols. Such dicarboxylic acids have a carboxyl group located on an adjacent carbon atom in the dicarboxylic acid, and a -CO-OR a21 It has two pairs of bases represented by .

[0134] Carboxylic group and -CO-OR a21 The above dicarboxylic acid, which has two pairs of groups represented by , has the position of the carboxyl group and -CO-OR a21 Isomers with different group positions can exist. The above dicarboxylic acid may be one of these isomers used alone, or two or more may be used in combination. As an example, with respect to the dicarboxylic acid corresponding to pyromellitic dianhydride, there are isomers represented by the following formulas (a4-a1) and (a4-a2). Furthermore, with respect to the dicarboxylic acid corresponding to 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, there are isomers represented by the following formulas (a4-b1), (a4-b2), and (a4-b3). In the following equations (a4-a1), (a4-a2), and (a4-b1) to (a4-b3), R a21 These are as described above.

[0135] [ka]

[0136] Examples of the dicarboxylic acids corresponding to the tetracarboxylic dianhydrides represented by the aforementioned formulas (a3-2) to (a3-4) include compounds represented by the following formulas (a4-2a) to (a4-2c), formulas (a4-3a) to (a4-3c), and formulas (a4-4a) to (a4-4c). In formulas (a4-2a) to (a4-2c), formulas (a4-3a) to (a4-3c), and formulas (a4-4a) to (a4-4c), R a01 ~R a05 are the same as these in formulas (a3-2) to (a3-4). In formulas (a4-2a) to (a4-2c), formulas (a4-3a) to (a4-3c), and formulas (a4-4a) to (a4-4c), R a21 is as described above.

Chemical formula

[0137] Examples of the dicarboxylic acids corresponding to the tetracarboxylic dianhydrides represented by the aforementioned formulas (a3-5) to (a3-7) include compounds represented by the following formulas (a4-5a) to (a4-5c), formulas (a4-6a) to (a4-6c), formula (a4-7a), and formula (a4-7b). In formulas (a4-5a) to (a4-5c), formulas (a4-6a) to (a4-6c), formula (a4-7a), and formula (a4-7b), R a01 ~R a03 , R a06 , m1, and m2 are the same as these in formulas (a3-5) to (a3-7). In formulas (a4-5a) to (a4-5c), formulas (a4-6a) to (a4-6c), formula (a4-7a), and formula (a4-7b), R a21 is as described above.

[0138]

Chemical formula

[0139] The reaction between tetracarboxylic dianhydrides and alcohols is usually carried out in an organic solvent. The organic solvent used in the reaction between tetracarboxylic dianhydrides and alcohols is not particularly limited as long as it can dissolve the tetracarboxylic dianhydrides and alcohols and does not react with them. The organic solvent can be used alone or in a mixture of two or more.

[0140] Examples of organic solvents used in the reaction of tetracarboxylic dianhydrides with alcohols include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutylamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylisobutyrateamide, methoxy-N,N-dimethylpropionamide, butoxy-N,N-dimethylpropionamide, N-methylcaprolactam, N,N'-dimethylpropyleneurea, N,N,N',N'-tetramethylurea, and pyridine; dimethyl sulfoxide; sulfolane; γ-butyrolactone, γ-valerolactone, δ-valero Examples include lactones such as lactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-caprolactone; esters such as methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate; carbonates such as ethylene carbonate and propylene carbonate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetonitrile; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, and o-dichlorobenzene; and hexane, heptane, benzene, toluene, and xylene. These organic solvents may be used individually or in combination of two or more.

[0141] Among these organic solvents, nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea are preferred.

[0142] The temperature at which the tetracarboxylic dianhydride reacts with alcohols is not particularly limited, as long as the reaction proceeds well. Typically, the reaction temperature between the tetracarboxylic dianhydride and alcohols is preferably -5°C to 120°C, more preferably 0°C to 80°C, and particularly preferably 0°C to 50°C. The reaction time between the tetracarboxylic dianhydride and alcohols varies depending on the reaction temperature, but is typically preferably 30 minutes to 20 hours, more preferably 1 hour to 8 hours, and particularly preferably 2 hours to 6 hours.

[0143] A small amount of polymerization inhibitor may be used to prevent crosslinking between ethylenically unsaturated double bonds during the reaction between tetracarboxylic dianhydride and alcohols. Examples of polymerization inhibitors include phenols such as hydroquinone, 4-methoxyphenol, tert-butylpyrocatechol, and bis-tert-butylhydroxytoluene, as well as phenothiazines. The amount of polymerization inhibitor used is preferably, for example, 0.01 mol% to 5 mol% relative to the number of moles of ethylenically unsaturated double bonds.

[0144] The reaction between tetracarboxylic dianhydrides and alcohols may be carried out in the presence of organic bases such as pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, and 1,4-azabicyclo[2,2,2]octane. These bases may be used individually or in combination of two or more.

[0145] The amount of alcohol used is preferably 1.8 moles to 2.2 moles per mole of tetracarboxylic dianhydride, and more preferably 2 moles to 2.1 moles.

[0146] In the production of dicarboxylic acids, depending on the production conditions, only one of the dicarboxylic acid anhydride groups may react with alcohols to produce a monocarboxylic acid compound having a dicarboxylic acid anhydride group, or a portion of the tetracarboxylic dianhydride may react with water in the reaction system to produce a tetracarboxylic acid compound or a tricarboxylic acid compound. Insofar as a polyamide resin can be obtained, a dicarboxylic acid comprising at least one selected from the above-mentioned monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds can be used in the production of the polyamide resin. If the dicarboxylic acid contains at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds as an impurity, the content of at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds as an impurity in the dicarboxylic acid is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 1% by mass or less, based on the mass of the dicarboxylic acid including the mass of the impurity.

[0147] [Other dicarboxylic acids] As mentioned above, in addition to the dicarboxylic acid, other dicarboxylic acids that do not fall under the category of the aforementioned dicarboxylic acids may also be used. These other dicarboxylic acids may be used individually or in combination of two or more.

[0148] As other dicarboxylic acids, various dicarboxylic acids that have been conventionally used as raw materials for polyamide resins can be used without any particular limitations. As dicarboxylic acids, aliphatic dicarboxylic acids having 2 to 50 carbon atoms and aromatic carboxylic acids having 8 to 50 carbon atoms are preferred.

[0149] Suitable examples of dicarboxylic acid compounds include adipic acid, sebacic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 4,4'-dicarboxybiphenyl, as well as alkyl, alkoxy, or halogen-substituted derivatives thereof. As the alkyl group used as a substituent, an alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group used as a substituent, an alkoxy group having 1 to 4 carbon atoms is preferred. When the aforementioned dicarboxylic acid compound is substituted with an alkyl group, an alkoxy group, or a halogen, the number of substitutions is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0150] <Method for producing polyamide resin> A polyamide resin is produced by polycondensing the above-mentioned dicarboxylic acid and a diamine compound in the presence of a compound (A) having a hydroxyl group or a thiol group. The pKa value of compound (A) is between 5.5 and 8.05. The pKa value is the value at 25°C. The pKa value can be measured by well-known methods such as titration. A high molecular weight polyamide resin can be produced by condensing the aforementioned dicarboxylic acid with the aforementioned diamine compound in the presence of the above compound (A).

[0151] In particular, since it is possible to produce polyamide resins with high molecular weight, the pKa value of the hydroxyl group or thiol group in compound (A) is preferably 5.5 or more and 6.0 or less.

[0152] Typically, polycondensation occurs in the presence of a condensing agent (B), or in the presence of a condensing agent (B) and a condensation aid (C). When polycondensation is carried out in the presence of a condensing agent (B) and in the absence of a condensation aid (C), the condensing agent (B) must contain a compound that produces the above-mentioned compound (A) under the reaction conditions of polycondensation. When polycondensation is carried out in the presence of a condensing agent (B) and a condensation aid (C), the condensing agent (B) contains a compound that produces the above-mentioned compound (A) under the reaction conditions of polycondensation, or the condensation aid (C) contains the above-mentioned compound (A) or a compound that produces the above-mentioned compound (A) under the reaction conditions of polycondensation.

[0153] Compounds that can be used as a condensing agent (B) and produce the above compound (A) under polycondensation reaction conditions include (1-cyano-2-ethoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate (COMU), 1-[bis(dimethylamino)methylene]-1-H-benzotriazolium 3-oxide hexafluorophosphate (HBTU), and 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU). The above COMU generates ethyl cyano(hydroxyimino)ethyl ester with a pKa of 5.66 under polycondensation conditions. The above HBTU generates 4-hydroxybenzotriazole with a pKa of 7.85 under polycondensation conditions. The above HATU generates 7-aza-1-hydroxybenzotriazole with a pKa of 7.01 under polycondensation conditions.

[0154] The compound that can be used as a condensing agent (B) and does not produce compound (A) under polycondensation reaction conditions is not particularly limited, and compounds that have been conventionally used as condensing agents in the production of polyamide resins can be used. Examples of such compounds include at least one selected from the group consisting of dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1-cyclohexyl-3-(2-morpholinoethyl)-carbodiimide-methotoluenesulfonate, 1,3-bis(2,2-dimethyl-1,3-dioxolan-4-ylmethyl)carbodiimide, polymer-supported 1-benzyl-3-cyclohexylcarbodiimide, and polymer-supported 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.

[0155] Examples of compounds (A) that can be used as condensation aids (C) include N-substituted imino compounds (Ac1) represented by the following formula (A-c1), N-substituted triazole compounds (Ac2) represented by the following formula (A-c2), N-substituted dihydrotriazinon compounds represented by the following formula (A-c3), and 2-hydroxy-5-nitropyridine. [ka]

[0156] In equation (A-c1), R c1 , and R c2 These are each independently monovalent organic groups. c1 , and R c2 At least one of them is a cyano group or an alkoxycarbonyl group. c3 R is a hydroxyl group or a thiol group. c3 The hydroxyl group or thiol group may be protected by a protecting group that can be removed under polycondensation conditions. Under polycondensation conditions, the protected hydroxyl group or thiol group yields a hydroxyl group or thiol group upon removal of the protecting group.

[0157] R c1 , and R c2Organic groups other than cyano groups and alkoxycarbonyl groups may include heteroatoms such as O, N, S, P, B, and halogen atoms. c1 , and R c2 If the organic group is an organic group other than a cyano group or an alkoxycarbonyl group, it is preferable that the organic group is a hydrocarbon group. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. R c1 , and R c2 The number of carbon atoms in the organic groups other than the cyano group and the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 8. Specific examples of organic groups other than cyano groups and alkoxycarbonyl groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and n-octyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and aryl groups such as phenyl, naphthalene-1-yl, naphthalene-2-yl, 2-phenylphenyl, 3-phenylphenyl, and 4-phenylphenyl.

[0158] R c1 , and R c2 The number of carbon atoms in the alkoxy group within the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 9. The number of carbon atoms in the alkoxy group contained within the alkoxycarbonyl group is preferably 1 to 8. c1 , and R c2Preferred specific examples of alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, and n-octyloxycarbonyl group.

[0159] In equation (A-c1), R c3 R is a hydroxyl group or a thiol group. c3 Examples of protecting groups that may be present in a hydroxyl group or thiol group include -PO(OR c4 A diarykoxyphosphoryl group represented by )2 is an example. c4 R is an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms. c4 Preferred examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

[0160] Suitable examples of the N-substituted imino compound (Ac1) represented by formula (A-c1) include cyano(hydroxyimino)ethyl acetate, 2-hydroxyimino-2-phenylacetonitrile, and hydroxyiminomalonate diethyl ester.

[0161] In equation (A-c2), R c4 , and R c5 Each of these is independently a hydrogen atom or a monovalent organic group. c4 , and R c5 If both are organic groups, R c4 , and R c5 They may bond to each other to form a ring. c6 R is a hydroxyl group or a thiol group. c6The hydroxyl group or thiol group may be protected by a protecting group that can be removed under polycondensation conditions. Under polycondensation conditions, the protected hydroxyl group or thiol group yields a hydroxyl group or thiol group upon removal of the protecting group.

[0162] R c4 , and R c5 The organic group may include heteroatoms such as O, N, S, P, B, and halogen atoms. c4 , and R c5 If the organic group is an organic group, examples of such organic groups include alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkoxy groups, aryl groups, aryloxy groups, aliphatic acyl groups, aromatic acyl groups, aliphatic acyloxy groups, aromatic acyloxy groups, alkoxycarbonyl groups, and aryloxycarbonyl groups.

[0163] R c4 , and R c5 The number of carbon atoms in the organic group is not particularly limited, but it is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 8.

[0164] Preferred specific examples of alkyl groups as organic groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and n-octyl groups.

[0165] Preferred examples of cycloalkyl groups as organic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0166] Preferred specific examples of alkoxy groups as organic groups include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, and n-octyloxy group.

[0167] Preferred examples of cycloalkoxy groups as organic groups include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, and cyclooctyloxy group.

[0168] Preferred examples of aryl groups as organic groups include phenyl groups, naphthalen-1-yl groups, naphthalen-2-yl groups, 2-phenylphenyl groups, 3-phenylphenyl groups, and 4-phenylphenyl groups.

[0169] Preferred specific examples of aryloxy groups as organic groups include phenoxy group, naphthalene-1-yloxy group, naphthalene-2-yloxy group, 2-phenylphenoxy group, 3-phenylphenoxy group, and 4-phenylphenoxy group.

[0170] Preferred examples of aliphatic acyl groups as organic groups include acetyl groups, propionyl groups, butanoyl groups, pentanoyl groups, hexanoyl groups, heptanol groups, and octanoyl groups.

[0171] Preferred examples of aromatic acyl groups as organic groups include benzoyl group, naphthalene-1-ylcarbonyl group, naphthalene-2-ylcarbonyl group, 2-phenylbenzoyl group, 3-phenylbenzoyl group, and 4-phenylbenzoyl group.

[0172] Preferred specific examples of aliphatic acyloxy groups as organic groups include acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanyloxy, and octanoyloxy groups.

[0173] Preferred specific examples of aromatic acyloxy groups as organic groups include benzoyloxy groups, naphthalene-1-ylcarbonyloxy groups, naphthalene-2-ylcarbonyloxy groups, 2-phenylbenzoyloxy groups, 3-phenylbenzoyloxy groups, and 4-phenylbenzoyloxy groups.

[0174] Preferred specific examples of alkoxycarbonyl groups as organic groups include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, and n-octyloxycarbonyl group.

[0175] Preferred specific examples of aryloxycarbonyl groups as organic groups include phenoxycarbonyl group, naphthalene-1-yloxycarbonyl group, naphthalene-2-yloxycarbonyl group, 2-phenylphenoxycarbonyl group, 3-phenylphenoxycarbonyl group, and 4-phenylphenoxycarbonyl group.

[0176] R c4 , and R c5 When organic groups are bonded to each other to form a ring, the ring may be monocyclic or polycyclic. The ring may be an aliphatic ring, an aromatic ring, or a combination of an aliphatic ring and an aromatic ring. The ring may be a hydrocarbon ring or a heterocycle. Examples of heteroatoms included in the heterocycle include N, O, and S. If the ring is between aliphatic atoms, the aliphatic ring may have an oxo group (=O) on a carbon atom.

[0177] R c4 , and R c5The ring formed may have substituents. Examples of substituents include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, alkylthio groups having 1 to 4 carbon atoms, alkylsulfonyl groups having 1 to 4 carbon atoms, alkoxycarbonyl groups having 2 to 5 carbon atoms, halogenated alkyl groups having 1 to 4 carbon atoms, alkanoyl groups having 2 to 5 carbon atoms, alkanoyloxy groups having 2 to 5 carbon atoms, halogen atoms, nitro groups, and cyano groups. R c4 , and R c5 When the ring formed has substituents, the number of substituents is not particularly limited. The number of substituents is proportional to the number of atoms that make up the ring.

[0178] R c4 , and R c5 Specific examples of rings formed by this include benzene rings, methylbenzene rings, dimethylbenzene rings, dimethylbenzene rings, methoxybenzene rings, ethoxybenzene rings, methoxycarbonylbenzene rings, ethoxycarbonylbenzene rings, nitrobenzene rings, methylsulfonylbenzene rings, ethylsulfonylbenzene rings, trifluoromethylbenzene rings, chlorobenzene rings, bromobenzene rings, iodobenzene rings, tetrachlorobenzene rings, tetrabromobenzene rings, tetrafluorobenzene rings, naphthalene rings, pyridine rings, pyrimidine rings, pyridazine rings, quinoline rings, isoquinoline rings, imidazole rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, 1,2,3,4-tetrahydronaphthalene rings, 1,2,3,4-tetrahydronaphthalene-1,4-dione rings, and decalin rings.

[0179] The following compounds are suitable examples of N-substituted imino compounds (Ac2) represented by formula (A-c2). [ka]

[0180] In equation (A-c3), R c7 , and R c8Each of these is independently a hydrogen atom or a monovalent organic group. c7 , and R c8 If both are organic groups, R c7 , and R c8 They may bond to each other to form a ring. c9 R is a hydroxyl group or a thiol group. c6 The hydroxyl group or thiol group may be protected by a protecting group that can be removed under polycondensation conditions. Under polycondensation conditions, the protected hydroxyl group or thiol group yields a hydroxyl group or thiol group upon removal of the protecting group.

[0181] R c7 , and R c8 As an organic group, and R c7 , and R c8 The ring formed by is R c4 , and R c5 As an organic group, and R c4 , and R c5 It is similar to the ring formed by [the two entities].

[0182] The following compounds are suitable examples of N-substituted dihydrotriazinon compounds (Ac3) represented by formula (A-c3). [ka]

[0183] Among the methods described above, the method of polycondensation in the presence of a condensation aid (C) containing cyano(hydroxyimino)ethyl ester and a condensation agent (B) is preferred due to the ease of obtaining the condensation agent (B) and the ease of producing high molecular weight polyamide resins.

[0184] The amount of condensing agent (B) used is not particularly limited as long as a polyamide resin of the desired molecular weight can be obtained. Typically, the amount of condensing agent (B) used is preferably 1 mole to 5 moles, more preferably 2 moles to 4 moles, and even more preferably 2 moles to 3 moles, per mole of dicarboxylic acid.

[0185] The amount of condensation aid (C) used is not particularly limited as long as a polyamide resin of the desired molecular weight can be obtained. Typically, the amount of condensation aid (C) used is preferably 1 mole to 5 moles, more preferably 2 moles to 4 moles, and even more preferably 2 moles to 3 moles, per mole of dicarboxylic acid.

[0186] Specifically, a polyamide resin is obtained by reacting a dicarboxylic acid and a diamine compound in an organic solvent in the presence of a condensing agent (B), or a condensing agent (B) and a condensing aid (C), at a temperature of, for example, -20°C to 150°C, preferably 0°C to 50°C, for 30 minutes to 24 hours, preferably 1 hour to 4 hours.

[0187] As the solvent used in the polycondensation, the aforementioned solvents that can be used in the reaction between tetracarboxylic dianhydrides and alcohols can be used. The amount of solvent used is preferably 50 parts by mass or more and 10,000 parts by mass or less, more preferably 100 parts by mass or more and 2,000 parts by mass or less, and even more preferably 150 parts by mass or more and 1,000 parts by mass or less, based on 100 parts by mass of the total mass of the dicarboxylic acid and the diamine compound.

[0188] The amount of dicarboxylic acid and diamine compound used in the production of polyamide resin is not particularly limited, but it is preferable to use 0.8 moles to 1.2 moles of diamine compound per mole of dicarboxylic acid, more preferably 0.9 moles to 1.1 moles, and particularly preferably 0.95 moles to 1.05 moles.

[0189] Polycondensation is carried out until the weight-average molecular weight of the resulting polyamide resin increases to the desired level. Polycondensation is carried out until the weight-average molecular weight of the polyamide resin is preferably 30,000 or more, more preferably 40,000 or more, and even more preferably 50,000 or more. Here, the weight-average molecular weight of the polyamide resin is the weight-average molecular weight in terms of polystyrene obtained by GPC (gelvameation chromatography). The weight-average molecular weight of the polyamide resin is preferably 100,000 or less, and more preferably 80,000 or less, in terms of the developability of the photosensitive resin composition containing the polyamide resin.

[0190] The main chain ends of the polyamide resin may be sealed with an end-capping agent. Examples of end-capping agents include monoamines, acid anhydrides, monocarboxylic acids, monoacid halides, and monoactive ester compounds. Known compounds can be used as monoamines for end-capping. Examples of monoamines include aromatic monoamines such as aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-hydroxyaniline, 4-hydroxyaniline, 3-aminothiophenol, and 4-aminothiophenol; aliphatic monoamines that may have a branched structure with 3 to 20 carbon atoms, such as hexylamine and octylamine; monoamines having an alicyclic structure, such as cyclohexylamine; and aminosilanes such as trimethoxyaminopropylsilane and triethoxyaminopropylsilane. Among acid anhydrides, monoacid halides, and monoactive ester compounds used as end-cap sealing agents, acid anhydrides are preferred. Known acid anhydrides and their derivatives can be used as acid anhydrides. Examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, xo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, succicic anhydride, maleic anhydride, nadic anhydride, and their derivatives.

[0191] The polyamide resin produced as described above is separated and recovered from the reaction solution in the form of a solution or suspension, or by known methods, and then used for various applications.

[0192] As described above, the inventors provide the following (1) to (8). (1) A method for producing a polyamide resin, comprising generating a polyamide resin by polycondensation of a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and alcohols, and a diamine compound, Polyamide resin is given by the following formula (1): [ka] (In formula (1), X 1 , and Y 1 Each of these is an organic group having 6 to 40 carbon atoms, and R 1 , and R 2 Each of these is an organic group with 3 to 20 carbon atoms. It consists of constituent units represented by, The polycondensation is carried out in the presence of compound (A) having a hydroxyl group or a thiol group. A method for producing compound (A) such that the pKa value is between 5.5 and 8.05. (2) Compound (A) has a hydroxyl group or a thiol group, A method for producing a polyamide resin according to (1), wherein the pKa value of the hydroxyl group or thiol group in compound (A) is 5.5 or more and 6.0 or less. (3) Polycondensation is carried out in the presence of condensing agent (B), or in the presence of condensing agent (B) and condensing aid (C). A method for producing a polyamide resin according to (1) or (2), wherein the condensing agent (B) contains a compound that produces compound (A) under polycondensation reaction conditions, or the condensation aid (C) contains compound (A). (4) Polycondensation is carried out in the presence of a condensing agent (B) and a condensation aid (C). A method for producing a polyamide resin according to any one of (1) to (3), wherein the condensation aid (C) contains cyano(hydroxyimino)ethyl acetate as compound (A). (5) A method for producing a polyamide resin according to (3) or (4), wherein the condensing agent (B) is at least one selected from the group consisting of dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1-cyclohexyl-3-(2-morpholinoethyl)-carbodiimide-methotoluenesulfonate, 1,3-bis(2,2-dimethyl-1,3-dioxolan-4-ylmethyl)carbodiimide, polymer-supported 1-benzyl-3-cyclohexylcarbodiimide, and polymer-supported 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide. (6) The diamine compound is of the following formula (A1): [ka] (In formula (A1), X is an organic group having 1 or more carbon atoms and 100 or less, R a1 R is a hydroxyl group, a carboxyl group, or a halogen atom. a2 is an aliphatic group, hydroxyl group, carboxyl group, sulfonic acid group, or halogen atom having 1 to 20 carbon atoms, and Ar is R a2 A phenyl group which may be substituted with, or R a2 The naphthyl group may be substituted with ma1, where ma1 is an integer between 0 and 10 (inclusive), ma2 is an integer between 0 and 7 (inclusive), and ma3 is an integer between 1 and 10 (inclusive). Diamine compound (A-1), represented by the following formula (A2): [ka] (In formula (A2), R a3 and R a4 Each of these is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and ma4 and ma5 are independently integers between 0 and 4. Diamine compound (A-2), which has a substructure represented by the following formula (A3), and does not fall under diamine compound (A-1): [ka] (In formula (A3), R a5 and R a6 Each is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and ma6 and ma7 are independently integers between 0 and 4, R a7 and R a8 Each of these is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R a7 and R a8 They may also be joined together to form a ring. A method for producing a polyamide resin according to any one of (1) to (5), comprising having a substructure represented by and including one or more selected from the group consisting of diamine compound (A-1), diamine compound (A-3) which does not fall under diamine compound (A-2), and dimer amine compound (A4). (7) A method for producing a polyamide resin according to any one of (1) to (6), wherein polycondensation of a dicarboxylic acid and a diamine compound is carried out until the weight-average molecular weight of the resulting polyamide resin is 50,000 or more. [Examples]

[0193] The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0194] In Examples 1 to 9 and Comparative Examples 1 to 4, the following DA1 to DA3 were used as diamine compounds. [ka]

[0195] In Examples 1 to 9 and Comparative Examples 1 to 4, the following TC1 to TC3 were used as diamine compounds. [ka]

[0196] In Examples 1 to 9 and Comparative Examples 1 to 4, the following condensing agent (B) was used. COMU and HBTU are compounds that produce the aforementioned compound (A) under polycondensation conditions. DCC: Dicyclohexylcarbodiimide COMU: (1-cyano-2-ethoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate (COMU) HBTU: 1-[bis(dimethylamino)methylene]-1-H-benzotriazolium 3-oxide hexafluorophosphate DBOP: (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate diphenyl

[0197] In Examples 1-5, 7, 9, and Comparative Examples 1-3, the following compounds were used as condensation aids (C). Oxyma, NHP, and HOAt are compounds corresponding to compound (A) mentioned above. Oxyma: Cyano(hydroxyimino)ethyl ester NHP: 2-hydroxy-5-nitropyridine HOAt: 1-Hydroxy-7-Azabenzotriazole 2MP:2-mercaptopyridine HONB:N-hydroxy-5-norbornene-2,3-dicarboximide 2MBT: 2-mercaptobenzothiazole

[0198] [Examples 1-9 and Comparative Examples 1-4] 0.10 moles of the tetracarboxylic dianhydride of the type listed in Table 1 were dissolved in 69 g of N-methyl-2-pyrrolidone (NMP). To the resulting solution, 26.03 g (0.20 moles) of 2-hydroxyethyl methacrylate (HEMA), 15.82 g (0.20 moles) of pyridine, and 2.443 g (0.02 moles) of dimethylaminopyridine were added. The solution was then stirred at room temperature for 16 hours to obtain a dicarboxylic acid, which is the reaction product of tetracarboxylic dianhydride and 2-hydroxyethyl methacrylate (HEMA).

[0199] In Examples 1-5, 7, 9, and Comparative Examples 1-3, the dicarboxylic acid solution containing 0.1 moles of the obtained dicarboxylic acid was cooled to 0°C, and then a solution consisting of 0.21 moles of condensing agent (B) of the type listed in Table 1 and 42 g of NMP, 0.21 moles of condensing aid (C) of the type listed in Table 1 and 0.1 mole of a diamine compound of the type listed in Table 1 were added dropwise to the dicarboxylic acid solution. In Examples 6, 8, and Comparative Example 4, the dicarboxylic acid solution containing 0.1 moles of the obtained dicarboxylic acid was cooled to 0°C, and then a solution consisting of 0.21 moles of the type of condensing agent (B) listed in Table 1 and 42 g of NMP, along with 0.1 moles of the type of diamine compound listed in Table 1, was added dropwise to the dicarboxylic acid solution. After the dropwise addition was complete, the resulting reaction solution was stirred at room temperature for 4 hours to carry out the condensation reaction. After the reaction was complete, 19.7 g of methanol was added to the reaction solution, and the precipitate was removed by filtration to obtain the reaction solution. The obtained reaction solution was added dropwise to an aqueous solution of isopropyl alcohol to precipitate a brown polyamide resin powder. The precipitated powder was collected by filtration and washed three times with isopropyl alcohol. The washed powder was dried under reduced pressure to obtain the polyamide resin. Table 1 shows the weight-average molecular weight of the obtained polyamide resins, measured by gel permeation chromatography, in terms of polystyrene equivalent. Note that the pKa values ​​in Table 1 below represent the pKa of the compound generated under polycondensation conditions using either the condensation aid (C) or the condensation agent (B).

[0200] [Table 1]

[0201] A comparison of the examples with the comparative examples shows that a high molecular weight polyamide resin can be produced by polycondensation of a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and alcohols, with a diamine compound in the presence of compound (A) having a pKa value of 5.5 to 8.05.

Claims

1. A method for producing a polyamide resin, comprising generating a polyamide resin by polycondensation of a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and alcohols, and a diamine compound, The polyamide resin is defined by the following formula (1): 【Chemistry 1】 (In formula (1), X A1 and Y A1 are each independently organic groups having 6 to 40 carbon atoms, and R A1 and R A2 are each independently organic groups having 3 to 20 carbon atoms.) It consists of constituent units represented by, The polycondensation described above is carried out in the presence of a condensing agent (B). A method for producing a compound in which the condensing agent (B) comprises one or more compounds selected from the group consisting of (1-cyano-2-ethoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate and 1-[bis(dimethylamino)methylene]-1-H-benzotriazolium 3-oxide hexafluorophosphate.

2. A method for producing a polyamide resin, comprising generating a polyamide resin by polycondensation of a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and alcohols, and a diamine compound, The polyamide resin is defined by the following formula (1): 【Chemistry 2】 (In formula (1), X A1 and Y A1 are each independently organic groups having 6 to 40 carbon atoms, and R A1 and R A2 are each independently organic groups having 3 to 20 carbon atoms.) It consists of constituent units represented by, The polycondensation described above is carried out in the presence of a condensing agent (B) and a condensation aid (C). The condensing agent (B) comprises one or more compounds selected from the group consisting of dicyclohexylcarbodiimide, (1-cyano-2-ethoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate, and 1-[bis(dimethylamino)methylene]-1-H-benzotriazolium 3-oxide hexafluorophosphate. A method for producing a compound in which the condensation aid (C) comprises one or more compounds selected from the group consisting of cyano(hydroxyimino)ethyl acetate, 2-hydroxy-5-nitropyridine, and 1-hydroxy-7-azabenzotriazole.

3. The aforementioned diamine compound is of the following formula (A1): 【Transformation 3】 (In formula (A1), X is an organic group having 1 or more carbon atoms and 100 or less, R ａ１ R is a hydroxyl group, a carboxyl group, or a halogen atom. ａ２ is an aliphatic group, hydroxyl group, carboxyl group, sulfonic acid group, or halogen atom having 1 to 20 carbon atoms, and Ar is R ａ２ A phenyl group which may be substituted with, or R ａ２ The naphthyl group may be substituted with a different integer, where ma1 is an integer between 0 and 10, ma2 is an integer between 0 and 7, and ma3 is an integer between 1 and 10. Diamine compound (A-1), represented by the following formula (A2): 【Chemistry 4】 (In formula (A2), R ａ３ and R ａ４ Each of these is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and ma4 and ma5 are independently integers between 0 and 4. Diamine compound (A-2) having a substructure represented by the following formula (A3), which does not correspond to the diamine compound (A-1): 【Transformation 5】 (In formula (A3), R ａ５ and R ａ６ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, ma6 and ma7 are each independently an integer of 0 or more and 4 or less, R ａ７ and R ａ８ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R ａ７ and R ａ８ may be bonded to each other to form a ring.) A method for producing a polyamide resin according to claim 1 or 2, comprising having a substructure represented by and including one or more selected from the group consisting of the diamine compound (A-1), a diamine compound (A-3) that does not fall under the diamine compound (A-2), and a dimer amine compound (A4).

4. A method for producing a polyamide resin according to claim 1 or 2, wherein the polycondensation of the dicarboxylic acid and the diamine compound is carried out until the weight-average molecular weight of the resulting polyamide resin is 50,000 or more.

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