Fluorinated polyamide compound, fluorinated polyimide compound, curable composition, and cured product

Abstract

To provide a fluorinated polyamide compound which yields a cured product having both low dielectric loss tangent characteristics and solvent resistance, and to provide a similar fluorinated polyimide compound and a similar curable composition.SOLUTION: The present invention provides a fluorinated polyamide compound represented by formula (1), and a fluorinated polyimide compound represented by formula (3).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a fluorinated polyamide compound, a fluorinated polyimide compound, a curable composition, and a cured product. [Background technology]

[0002] Patent Document 1 describes a fluorinated nitrogen-containing heterocycle-containing compound having a repeating unit represented by the following formula: [ka] (In the above formula, n is an integer of 4 to 8, Rf is a single bond, -SO 2 -, -O-, -CO-, a divalent non-fluorinated organic group or a divalent fluorinated organic group, and ring C represents an imide ring or a benzimidazole ring which may have a substituent. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-178956 Summary of the Invention [Problem to be solved by the invention]

[0004] Such fluorinated nitrogen-containing heterocycle-containing compounds (polyimide compounds) are widely used industrially in the field of electronic materials due to their excellent thermal properties, mechanical properties, and chemical stability. For example, they are used as flexible printed circuit boards (FPCs), rewiring layers, and buffer coating films for semiconductors. In recent years, with the increasing integration of semiconductors, polyimide compounds are required to have low dielectric properties. In addition, solvent resistance is required to accommodate diversifying manufacturing processes.

[0005] However, with conventional techniques, it has been difficult to achieve both low dielectric properties and solvent resistance in a polyimide compound.

[0006] In view of this, the present disclosure provides a fluorinated polyamide compound capable of obtaining a cured product that has both low dielectric tangent characteristics and solvent resistance. The present disclosure provides a fluorinated polyimide compound capable of obtaining a cured product that has both low dielectric tangent characteristics and solvent resistance. The present disclosure provides a curable composition capable of obtaining a cured product that has both low dielectric tangent characteristics and solvent resistance. The present disclosure provides a cured product that has both low dielectric tangent characteristics and solvent resistance. [Means for solving the problem]

[0007] An embodiment of the present disclosure is a fluorinated polyamide compound represented by the following chemical formula (1) or the following chemical formula (2).

[0008] [ka] (In formula (1), m is the average degree of polymerization of the repeating unit represented by [], n is an integer of 1 to 8, ring A and ring B are independently a group having a hydrocarbon ring having or without a substituent, R is independently a hydrogen atom, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, R 1 each independently represents a hydroxyl group, a linear or branched alkoxy group which may have a substituent, an aromatic oxy group which may have a substituent, or a halogen atom; L represents a linking group; X independently represents a monovalent organic group having an unsaturated carbon bond; R 2 R 1 or the group represented by X.

[0009] [ka] (In formula (2), m represents the average degree of polymerization of the repeating unit represented by []; Y represents independently a monovalent organic group having an unsaturated carbon bond; n represents a ring A, a ring B, R, L, and R 1 is as mentioned above.)

[0010] In formula (1) or formula (2), X and Y are preferably monovalent organic groups having a styryl group.

[0011] Another aspect of the present disclosure is a fluorinated polyimide compound represented by the following chemical formula (3), the following chemical formula (4), or the following chemical formula (5).

[0012] [ka] (In formula (3), m is the average degree of polymerization of the repeating unit represented by [], n is an integer of 1 to 8, ring A and ring B are independently a group having a hydrocarbon ring having or without a substituent, R is independently a hydrogen atom, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, L is a linking group, X is independently a monovalent organic group having an unsaturated carbon bond, R 2 each independently represents a hydroxyl group, a linear or branched alkoxy group which may have a substituent, an aromatic oxy group which may have a substituent, a halogen atom, or the group represented by X.

[0013] [ka] (In formula (4), X' is independently a monovalent organic group having an unsaturated carbon bond, and m, n, ring A, ring B, R and L are as defined above.)

[0014] [ka] (In formula (5), m is the average degree of polymerization of the repeating units represented by [ ], Y is independently a monovalent organic group having an unsaturated carbon bond, and n, ring A, ring B, R and L are as defined above.)

[0015] In the formula (3), (4), or (5), X, X', and Y are preferably monovalent organic groups having a styryl group.

[0016] Yet another aspect of the present disclosure is a curable composition, comprising at least one of the fluorinated polyamide compound and the fluorinated polyimide compound, and a radical polymerization initiator.

[0017] The curable composition of the present disclosure preferably further comprises a filler.

[0018] In the curable composition of the present disclosure, the content of the filler in the entire curable composition is preferably 10% by mass or more.

[0019] The curable composition of the present disclosure preferably further comprises a crosslinker.

[0020] Yet another aspect of the present disclosure is a cured product formed from the curable composition. Effect of the Invention

[0021] The present disclosure can provide a fluorinated polyamide compound capable of obtaining a cured product having both low dielectric tangent characteristics and solvent resistance. The present disclosure can provide a fluorinated polyimide compound capable of obtaining a cured product having both low dielectric tangent characteristics and solvent resistance. The present disclosure can provide a curable composition capable of obtaining a cured product having both low dielectric tangent characteristics and solvent resistance. The present disclosure can provide a cured product having both low dielectric tangent characteristics and solvent resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Hereinafter, when an upper limit value and a lower limit value are separately described, it is deemed that a numerical range combining any upper limit value and any lower limit value is substantially disclosed.

[0023] When a compound is described, all its isomers are also described.

[0024] The number average molecular weight (Mn) and weight average molecular weight (Mw) were determined by gel permeation chromatography (GPC) using a Shodex K-805L column at 40°C, a flow rate of 1 mL / min, chloroform as the eluent, and polystyrene as the standard.

[0025] The "substituent" is not particularly limited, and unless otherwise specified, examples thereof include a hydroxyl group, a halogen group, a thiol group, a sulfo group, an amino group, an imino group, a hydroxyamino group, a nitro group, a nitroso group, a carboxy group, a thiocarboxy group, an ester group, a thioester group, an aldehyde group, an acetyl group, and the like.

[0026] The term "aromatic" is not particularly limited, and unless otherwise specified, also includes heterocycles.

[0027] Specific embodiments of the present disclosure will be described in detail below, but the present disclosure is not limited to the following embodiments.

[0028] 1. Fluorinated polyamide compounds The fluorinated polyamide compound of this embodiment is represented by formula (1) or formula (2).

[0029] [ka] (In formula (1), m is the average degree of polymerization of the repeating unit represented by [], n is an integer of 1 to 8, ring A and ring B are independently a group having a hydrocarbon ring having or without a substituent, R is independently a hydrogen atom, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, R 1 each independently represents a hydroxyl group, a linear or branched alkoxy group which may have a substituent, an aromatic oxy group which may have a substituent, or a halogen atom; L represents a linking group; X independently represents a monovalent organic group having an unsaturated carbon bond; R 2 R 1or any of the groups represented by X above.

[0030] [ka] (In formula (2), m represents the average degree of polymerization of the repeating unit represented by []; Y represents independently a monovalent organic group having an unsaturated carbon bond; n represents a ring A, a ring B, R, L, and R 1 is as mentioned above.)

[0031] In the fluorinated polyamide compound of this embodiment represented by formula (1) or formula (2), ring A is a linear perfluoroalkylene group (-(CF 2 ) n -) is bonded. Therefore, the fluorinated polyimide compound derived from the fluorinated polyamide compound of this embodiment represented by formula (1) or formula (2) has a lower dielectric tangent than conventional ones and exhibits excellent low dielectric properties. In addition, the fluorinated polyamide compound of this embodiment exhibits excellent solubility in organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide.

[0032] In formula (1), m represents the average degree of polymerization of the repeating units represented by [ ]. The average degree of polymerization m is preferably 500 or less, more preferably 300 or less, and further preferably 200 or less, and may be 2 or more, or may be 3 or more. The average degree of polymerization m is calculated from the number average molecular weight (Mn) of the fluorinated polyamide compound of this embodiment.

[0033] Since the dielectric constant and dielectric tangent of the fluorinated polyimide compound derived from the fluorinated polyamide compound of this embodiment can be further reduced, the fluorinated polyamide compound of this embodiment may be a polymer having a relatively large average polymerization degree m, for example, a polymer having an average polymerization degree m of more than 100.

[0034] In formula (2), m represents the average degree of polymerization of the repeating units represented by [ ]. Since m in formula (2) is the same as the average degree of polymerization m in formula (1) described above, the explanation will be omitted.

[0035] n represents an integer of 1 to 8. n is preferably an integer of 4 to 8, and more preferably an integer of 4 to 6, since the dielectric constant and dielectric dissipation factor of the fluorinated polyimide compound derived from the fluorinated polyamide compound can be further reduced.

[0036] Ring A is a group having a hydrocarbon ring with or without a substituent. The hydrocarbon ring constituting ring A is preferably a cyclohexane ring, a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, or an anthracene ring, and more preferably a benzene ring. Examples of the group having a benzene ring include a phenyl group, a biphenyl group, and a terphenyl group. The number of carbon atoms in ring A is preferably 6 to 20, and more preferably 6 to 15.

[0037] Ring B is a group having a hydrocarbon ring with or without a substituent. The hydrocarbon ring constituting ring B is preferably a cyclohexane ring, a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, or an anthracene ring, and more preferably a benzene ring. Examples of the group having a benzene ring include a phenyl group, a biphenyl group, and a terphenyl group. The number of carbon atoms in ring B is preferably 6 to 20, and more preferably 6 to 15.

[0038] R is independently hydrogen, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group. Hydrogen is preferred as R.

[0039] R 1 are independently a hydroxyl group, a linear or branched alkoxy group which may have a substituent, an aromatic oxy group which may have a substituent, or a halogen atom.

[0040] R 1The number of carbon atoms in the alkoxy group as the aryl group is preferably 1 to 12, and more preferably 1 to 6. The alkoxy group may contain a hydrocarbon group having an unsaturated carbon bond. Examples of the hydrocarbon group having an unsaturated carbon bond include an alkenyl group (such as a vinyl group or an allyl group), an acryloyl group, a methacryloyl group, and an alkynyl group.

[0041] R 1 The substituent that the alkoxy group and aromatic oxy group as may have is preferably an alkyl group, a fluorinated alkyl group, an alkoxy group, a fluorinated alkoxy group, a halo group (halogen atom), a nitro group, a cyano group or an ester group, more preferably an alkoxy group.

[0042] R 1 Examples of the aromatic oxy group as the aromatic oxy group include a phenoxy group having no substituent and a triazinyloxy group which may have a substituent.

[0043] R 1 may be, independently, a hydroxyl group, an unsubstituted phenoxy group, a methoxy group, an ethoxy group, a chlorine atom, or a compound represented by the following formula:

[0044] [ka]

[0045] L is a linking group. L can be a single bond, -O-, -SO 2 -, -CO-, a divalent non-fluorinated organic group or a divalent fluorinated organic group are preferred.

[0046] The non-fluorinated organic group is a divalent organic group that does not contain a fluorine atom. The non-fluorinated organic group is preferably a linear or branched non-fluorinated alkylene group or a non-fluorinated arylene group.

[0047] The fluorinated organic group is a divalent organic group having one or more fluorine atoms. The fluorinated organic group is preferably a linear or branched fluorinated alkylene group or a fluorinated arylene group.

[0048] A linear or branched fluorinated alkylene group can also be used as L, since it can further reduce the dielectric constant and dielectric loss tangent of the fluorinated polyimide compound derived from the fluorinated polyamide compound. The fluorinated alkylene group may be a perfluoroalkylene group, and the number of carbon atoms of the perfluoroalkylene group may be, for example, 1 to 8.

[0049] As the fluorinated alkylene group, a perfluoroalkylene group represented by the following formula may be used, since it is possible to further reduce the dielectric constant and dielectric tangent of a fluorinated polyimide compound derived from a fluorinated polyamide compound. Formula:-(CF 2 ) n1 - (In the formula, n1 represents an integer of 1 to 8.)

[0050] n1 may be an integer of 4 to 8, an integer of 4 to 6, or even 4 or 6, since this can further reduce the dielectric constant and dielectric tangent of the fluorinated polyimide compound derived from the fluorinated polyamide compound.

[0051] The fluorinated polyamide compound represented by formula (1) has crosslinking moieties X at both ends of the molecule. The fluorinated polyamide compound represented by formula (2) has crosslinking moieties Y at both ends of the molecule. Therefore, the fluorinated polyamide compound of this embodiment represented by formula (1) or formula (2) has crosslinking properties, and a cured product is obtained by crosslinking the fluorinated polyamide compound of this embodiment. Since the fluorinated polyamide compound of this embodiment has such a structure, the cured product obtained by crosslinking the fluorinated polyamide compound of this embodiment exhibits excellent solvent resistance while maintaining low dielectric properties.

[0052] In formula (1), X is independently a monovalent organic group having an unsaturated carbon bond. The monovalent organic group is a monovalent group containing a carbon atom, or a group formed by removing one hydrogen atom from an organic compound. Examples of the monovalent organic group include an aliphatic hydrocarbon group which may have a substituent, and an aromatic group which may have a substituent.

[0053] X may be a group having any structure as a whole as long as it has an unsaturated carbon bond and a carbon chain or a carbon ring as a basic skeleton, and may have one or more elements other than carbon as a constituent element. For example, hydrogen, oxygen, halogen, etc. may be mentioned. The carbon chain may be a straight chain or a branched chain having one or more side chains. The carbon number of X is preferably 2 to 15, more preferably 2 to 10.

[0054] Examples of X include organic groups having a styryl group, an alkenyl group (vinyl group, allyl group, etc.), an acryloyl group, a methacryloyl group, an alkynyl group, etc. Among these, an organic group having a styryl group is preferable.

[0055] In formula (1), X may be, for example, a monovalent organic group represented by *-O-X' or *-NH-X', and is preferably a monovalent organic group represented by *-NH-X'. * represents a bonding site with the main chain skeleton. When X is a monovalent organic group represented by *-NH-X', the molecular terminals can also be imidized (dehydration cyclization) by heating or the like, resulting in better heat resistance and low dielectric properties. X' is a monovalent organic group corresponding to the above-mentioned X.

[0056] In formula (2), Y is independently a monovalent organic group having an unsaturated carbon bond. The bonding mode between Y and the main chain is the same as that of the crosslinking site X in formula (1) described above, except that the bonding mode between Y and the main chain is different. For example, an amide bond can be mentioned as the bonding mode between Y and the main chain.

[0057] R 2 is R 1or X. 2 R 1 When R is a group represented by the formula (1), the degree of crosslinking can be increased appropriately. Therefore, the cured product obtained by crosslinking the fluorinated polyamide compound of the present embodiment represented by the formula (1) can have both solvent resistance and flexibility (elongation at break). 2 When R is a group represented by X, the fluorinated polyamide compound of this embodiment represented by formula (1) has two crosslinking sites X at each end of the molecule, and has a total of four crosslinking sites X. 2 R 1 Since the number of crosslinking sites X is greater than that in the case of a group represented by R 2 When is a group represented by X, the cured product obtained by crosslinking the fluorinated polyamide compound of this embodiment represented by formula (1) has better solvent resistance.

[0058] The fluorinated polyamide compound of this embodiment represented by formula (1) is preferably a compound represented by formula (1-1). [ka] (In formula (1-1), m, n, R 1 , L, X and R 2 is as described above.)

[0059] The compound represented by formula (1-1) can be suitably used as a precursor of a fluorinated polyimide compound represented by formula (3-1) or formula (4-1) described later. In addition, by crosslinking the fluorinated polyamide compound represented by formula (1-1), a cured product described later can be obtained, and the obtained cured product has both low dielectric properties and solvent resistance.

[0060] The fluorinated polyamide compound of this embodiment represented by formula (2) is preferably a compound represented by formula (2-1). [ka] (In formula (2-1), m, n, R1 , L and Y are as defined above.)

[0061] The compound represented by formula (2-1) can be suitably used as a precursor of a fluorinated polyimide compound represented by formula (5-1) described later. In addition, by crosslinking the fluorinated polyamide compound represented by formula (2-1), a cured product described later can be obtained, and the obtained cured product has both low dielectric properties and solvent resistance.

[0062] The number average molecular weight (Mn) of the fluorinated polyamide compound of this embodiment represented by formula (1) or formula (2) is preferably 2,000 or more, more preferably 10,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less.

[0063] The molecular weight distribution (Mw / Mn) of the fluorinated polyamide compound of this embodiment represented by formula (1) or formula (2) is preferably 1.5 or more, more preferably 2 or more, and preferably 5 or less, more preferably 4 or less.

[0064] The fluorinated polyamide compound of this embodiment represented by formula (1) can be suitably used as a precursor of the fluorinated polyimide compound represented by formula (3) or formula (4) described later. The fluorinated polyamide compound of this embodiment represented by formula (2) can be suitably used as a precursor of the fluorinated polyimide compound represented by formula (5) described later. In addition, by crosslinking the fluorinated polyamide compound of this embodiment represented by formula (1) or formula (2), a cured product described later can be obtained.

[0065] 2. Fluorinated polyimide compounds The fluorinated polyimide compound of the present embodiment is represented by formula (3), formula (4), or formula (5).

[0066] [ka] (In formula (3), m is the average degree of polymerization of the repeating unit represented by [], n is an integer of 1 to 8, ring A and ring B are independently a group having a hydrocarbon ring having or without a substituent, R is independently a hydrogen atom, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, L is a linking group, X is independently a monovalent organic group having an unsaturated carbon bond, R 2 each independently represents a hydroxyl group, a linear or branched alkoxy group which may have a substituent, an aromatic oxy group which may have a substituent, a halogen atom, or the group represented by X.

[0067] [ka] (In formula (4), X' is independently a monovalent organic group having an unsaturated carbon bond, and m, n, ring A, ring B, R and L are as defined above.)

[0068] [ka] (In formula (5), m is the average degree of polymerization of the repeating units represented by [ ], Y is independently a monovalent organic group having an unsaturated carbon bond, and n, ring A, ring B, R and L are as defined above.)

[0069] In the fluorinated polyimide compound of the present embodiment represented by formula (3), formula (4), or formula (5), ring A is a linear perfluoroalkylene group (-(CF 2 ) n -) is bonded. Therefore, the fluorinated polyimide compound of this embodiment represented by formula (3), formula (4), or formula (5) has a lower dielectric tangent than conventional ones, and exhibits excellent low dielectric properties. In addition, the fluorinated polyamide compound of this embodiment exhibits excellent solubility in organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide.

[0070] In formula (3), m, n, ring A, ring B, R, R 2 , L and X are the same as those in formula (1). By adopting a suitable structure similar to that in formula (1), the dielectric constant and dielectric tangent of the fluorinated polyimide compound of the present embodiment represented by formula (3) can be further reduced.

[0071] In formula (4), m, n, ring A, ring B, R and L are the same as those in formula (1). By making it into a suitable structure similar to that of formula (1), the dielectric constant and dielectric loss tangent of the fluorinated polyimide compound of the present embodiment represented by formula (4) can be further reduced. X' is the same as X' described above as the partial structure of X in formula (1).

[0072] In formula (5), n, ring A, ring B, R, L, and Y are the same as those in formula (2). By making it into a suitable structure similar to that of formula (2), the dielectric constant and dielectric loss tangent of the fluorinated polyimide compound of the present embodiment represented by formula (5) can be further reduced. In formula (5), m represents the average degree of polymerization of the repeating unit represented by [ ].

[0073] The fluorinated polyimide compound of this embodiment represented by formula (3) has a crosslinking site X at the molecular end. The fluorinated polyimide compound of this embodiment represented by formula (4) has a crosslinking site X' at the molecular end. The fluorinated polyimide compound of this embodiment represented by formula (5) has a crosslinking site Y at the molecular end. Therefore, the fluorinated polyimide compound of this embodiment represented by formula (3), formula (4), or formula (5) all have crosslinking properties, and a cured product can be obtained by crosslinking the fluorinated polyimide compound of this embodiment. Since the fluorinated polyimide compound of this embodiment has such a structure, the cured product obtained by crosslinking the fluorinated polyimide compound of this embodiment exhibits excellent solvent resistance while maintaining low dielectric properties.

[0074] The cross-linking site X of the fluorinated polyimide compound of this embodiment represented by formula (3) is the same as the cross-linking site X of the fluorinated polyamide compound of this embodiment represented by formula (1). The cross-linking site X' of the fluorinated polyimide compound of this embodiment represented by formula (4) has an unsaturated carbon bond like the cross-linking site X of the fluorinated polyamide compound of this embodiment represented by formula (1). The cross-linking site Y of the fluorinated polyimide compound of this embodiment represented by formula (5) is the same as the cross-linking site Y of the fluorinated polyamide compound of this embodiment represented by formula (2). Therefore, the fluorinated polyimide compound of this embodiment can provide a cured product that has both low dielectric properties and solvent resistance.

[0075] The fluorinated polyimide compound represented by formula (3) is preferably a compound represented by formula (3-1).

[0076] [ka] (In formula (3-1), m, n, L, X and R 2 is the same as equation (3).

[0077] The fluorinated polyimide compound represented by formula (4) is preferably a compound represented by formula (4-1).

[0078] [ka] (In formula (4-1), m, n, L and X' are the same as those in formula (4).)

[0079] The fluorinated polyimide compound represented by formula (5) is preferably a compound represented by formula (5-1).

[0080] [ka] (In formula (5-1), m, n, L and Y are the same as those in formula (5).)

[0081] The dielectric loss tangent (Df) at 10 GHz of the fluorinated polyimide compound of the present embodiment represented by formula (3), formula (4), or formula (5) is preferably 0.005 or less, and more preferably 0.0028 or less.

[0082] The glass transition temperature of the fluorinated polyimide compound of the present embodiment represented by formula (3), formula (4), or formula (5) is preferably 100° C. or higher, 150° C. or higher, or 200° C. or higher, etc. Also, it is preferably 350° C. or lower, 300° C. or lower, or 250° C. or lower, etc. The glass transition temperature is a value measured by differential scanning calorimetry (DSC) in the same manner as in the examples.

[0083] The number average molecular weight (Mn) of the fluorinated polyimide compound of the present embodiment represented by formula (3), formula (4), or formula (5) is preferably 2,000 or more, more preferably 10,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less.

[0084] The molecular weight distribution (Mw / Mn) of the fluorinated polyimide compound of the present embodiment represented by formula (3), formula (4), or formula (5) is preferably 1.5 or more, more preferably 2 or more, and is preferably 5 or less, more preferably 4 or less.

[0085] By crosslinking the fluorinated polyimide compound of this embodiment represented by formula (3), formula (4), or formula (5), a cured product described below can be obtained.

[0086] 3. Method for producing fluorinated polyamide compound The fluorinated polyamide compound of this embodiment represented by formula (1) or formula (2) can be produced by the following procedure. First, a compound represented by formula (6) and a compound represented by formula (7) described later are polymerized to obtain compound (A). Then, a residue at the molecular end of the obtained compound (A) is reacted with a compound represented by formula (8) or formula (9) described later. This introduces a crosslinking moiety X or a crosslinking moiety Y to the residue at the molecular end of compound (A), and the fluorinated polyamide compound of this embodiment represented by formula (1) or formula (2) can be suitably produced.

[0087] [ka] (In formula (6), n, ring A, R and R 1 In formula (6), the two adjacent -COR 1 is a compound that combines two -CO 1 may form a ring together with the two carbon atoms to which they are attached.)

[0088] [ka] (In formula (7), rings B and L are as described above. 3 each independently represents hydrogen or a monovalent organic group.

[0089] R 3 are independently hydrogen or a monovalent organic group. The monovalent organic group is a monovalent group containing a carbon atom, or a group formed by removing one hydrogen atom from an organic compound. Examples of the monovalent organic group include an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, an aliphatic hydrocarbon acyl group which may have a substituent, and an aromatic acyl group which may have a substituent.

[0090] Specific examples of the monovalent organic group include -CH 3 , -C 2 H 5 , -C3 H 7 Lower alkyl groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as -CF 3 , -C 2 F 5 , -CH 2 F, -CH 2 CF 3 , -CH 2 C 2 F 5 a fluorine atom-containing lower alkyl group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as a phenyl group (having no substituent); a benzyl group (having no substituent); -C 6 F 5 , -CH 2 C 6 F 5 A phenyl or benzyl group in which 1 to 5 hydrogen atoms are substituted with fluorine atoms such as -C 6 H 5-k (CF 3 ) k , -CH 2 C 6 H 5-k (CF 3 ) k (k is an integer from 1 to 5) 3 Examples of acyl groups include a phenyl group or a benzyl group in which 1 to 5 hydrogen atoms are substituted; an aliphatic acyl group such as an acetyl group or a pivaloyl group; an aromatic acyl group such as a benzoyl group or a methylbenzoyl group; a fluorinated acetyl group such as a fluoroacetyl group or a trifluoroacetyl group; and a fluorobenzoyl group or a trifluoromethylbenzoyl group.

[0091] R 3 are each independently preferably hydrogen or an aromatic group which may have a substituent, more preferably hydrogen or a phenyl group which may have a substituent, and further preferably hydrogen, an unsubstituted phenyl group, or a phenyl group substituted with a fluorine atom-containing alkyl group having 1 to 10 carbon atoms.

[0092] R 3 In terms of ease of polymerization with the compound represented by formula (7), hydrogen, a phenyl group having no substituent, or a phenyl group substituted with a fluorine atom-containing alkyl group having 1 to 10 carbon atoms is preferred.

[0093] Compound (A) has a repeating unit structure represented by the following formula (A1) or formula (A2) depending on the residue at the molecular chain terminal. When the molecular chain terminal of compound (A) has a residue of a compound represented by formula (6), compound (A) has a repeating unit structure represented by formula (A1). When the molecular chain terminal of compound (A) has a residue of a compound represented by formula (7), compound (A) has a repeating unit structure represented by formula (A2).

[0094] [ka] (In formula (A1), m, n, ring A, ring B, R, R 1 and L is as defined above.)

[0095] [ka] (In formula (A2), m, n, ring A, ring B, R, R 1 and L is as defined above.)

[0096] The compound represented by formula (6) is preferably a compound represented by formula (6-1), and the compound represented by formula (7) is preferably a compound represented by formula (7-1). Compound (a) is obtained by polymerizing the compound represented by formula (6-1) and the compound represented by formula (7-1).

[0097] [ka] (In formula (6-1), n ​​and R 1 In formula (6-1), the two adjacent -COR 1 is a compound that combines two -CO 1 may form a ring together with the two carbon atoms to which they are attached.)

[0098] [ka] (In formula (7-1), L is as defined above.)

[0099] The compound (a) has a repeating unit structure represented by the following formula (a1) or (a2). [ka] (In formula (a1), m, n, R 1 and L is as defined above.)

[0100] [ka] (In formula (a2), m, n, R 1 and L is as defined above.)

[0101] The polymerization of the compound represented by formula (6) and the compound represented by formula (7) can be carried out in a solvent. The solvent is preferably one that does not substantially react with the compound represented by formula (6) and the compound represented by formula (7), has the property of dissolving the compound represented by formula (6) and the compound represented by formula (7) well, and is also a good solvent for the compound (A). Examples of such a solvent include, but are not limited to, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 1,3-dimethylimidazolidone (DMI), tetramethylurea (TMU), N,N'-dimethylpropyleneurea (DMPU), cyclohexanone, cyclopentanone, sulfolane, tetrahydrofuran (THF), and acetone. Among them, N-methyl-2-pyrrolidone (NMP) and 1,3-dimethylimidazolidone (DMI) are preferred. The amount of these solvents used is usually 10 to 1000 mL, preferably 50 to 400 mL, per 0.1 mol of the compound represented by formula (6) or the compound represented by formula (7).

[0102] The polymerization can also be carried out in the presence of an additive. For example, inorganic salts such as lithium chloride and calcium chloride may be added to obtain a compound with a large molecular weight. Among them, lithium chloride is preferred as the additive. The amount of the additive added is preferably 10% by mass or less, more preferably 5% by mass or less, based on the amount of the solvent.

[0103] The polymerization can be carried out, for example, by dissolving either the compound represented by formula (6) or the compound represented by formula (7) in a solvent, adding the other compound to the resulting solution, and then reacting them while stirring under an inert atmosphere such as nitrogen. The polymerization temperature is preferably -50°C or higher, 0°C or higher, or 35°C or higher. Also, it is preferably 150°C or lower, 100°C or lower, or 80°C or lower. The polymerization time is preferably 0.1 to 50 hours, more preferably 1 to 24 hours.

[0104] The average degree of polymerization m of the repeating unit represented by [ ] in formula (1) or the average degree of polymerization m of the repeating unit represented by [ ] in formula (2) can be adjusted by changing the molar ratio of the compounds represented by formula (6) and formula (7) during polymerization, the concentration of the polymerization solution, the polymerization temperature, the polymerization time, etc.

[0105] When the molecular chain terminal of compound (A) has a residue of a compound represented by formula (6) {when compound (A) is represented by formula (A1)}, a fluorinated polyamide compound represented by formula (1) can be obtained by introducing a crosslinkable group. When the molecular chain terminal of compound (A) has a residue of a compound represented by formula (7) {when compound (A) is represented by formula (A2)}, a fluorinated polyamide compound represented by formula (2) can be obtained by introducing a crosslinkable group.

[0106] That is, depending on the residue at the molecular end of compound (A), either a fluorinated polyamide compound represented by formula (1) or a fluorinated polyamide compound represented by formula (2) is obtained. The residue at the molecular end of compound (A) can be adjusted by controlling the molar ratio of the compound represented by formula (6) and the compound represented by formula (7) fed during polymerization.

[0107] After the polymerization is completed, the reaction mixture may be poured into a poor solvent such as methanol or water to separate the polymer, and then the polymer may be purified by a reprecipitation method to remove by-products, inorganic salts, etc., to obtain a compound with high purity.

[0108] Next, the obtained compound (A) is reacted with a compound represented by formula (8) or formula (9) to introduce a crosslinking moiety X or a crosslinking moiety Y into the residue at the molecular terminal of compound (A).

[0109] R x -X 1 (8) (In formula (8), R x represents a monovalent group having a reactive group capable of reacting with the residue at the molecular terminal of the compound (A) represented by the formula (A1) (the residue of the compound represented by the formula (6)); 1 is a monovalent organic group having an unsaturated carbon bond.

[0110] R y -Y 1 (9) (In formula (9), R y represents a monovalent group having a reactive group capable of reacting with the residue at the molecular terminal of the compound (A) represented by formula (A2) (the residue of the compound represented by formula (7)); Y 1 is a monovalent organic group having an unsaturated carbon bond.

[0111] The compound represented by formula (8) or (9) each contains a monovalent group R having a reactive group capable of reacting with the residue at the molecular end of compound (A). x or R y Each of them has:

[0112] When the molecular chain terminal of compound (A) has a residue of a compound represented by formula (6) {when compound (A) is represented by formula (A1)}, the molecular terminal group of compound (A) and R x The reactive groups in the reactants react to add the compound represented by formula (8) to compound (A), thereby obtaining the fluorinated polyamide compound represented by formula (1). 1 and X may have different structures or may have the same structure. 1 The structure of and X may differ due to the addition of a compound represented by formula (8) to compound (A).

[0113] When the molecular chain terminal of compound (A) has a residue of a compound represented by formula (7) {when compound (A) is represented by formula (A2)}, the molecular terminal group of compound (A) and R y The reactive groups in react to add the compound represented by formula (9) to compound (A), thereby obtaining the fluorinated polyamide compound represented by formula (2). 1 Y and Y may have different structures or may have the same structure. 1 The structure of and Y may differ due to the addition of a compound represented by formula (9) to compound (A).

[0114] R x or R y Examples of reactive groups that R has include a hydroxyl group, a carboxyl group, an acid anhydride group (-CO-O-CO-), and an amino group. x The reactive group of R is preferably a hydroxyl group or an amino group. y The reactive group possessed by the compound is preferably a carboxy group or an acid anhydride group.

[0115] Examples of the compound represented by formula (8) or formula (9) include aminostyrenes (e.g., 4-aminostyrene), carboxystyrenes (e.g., 4-carboxystyrene), vinylphenols (e.g., 4-vinylphenol), vinylbenzyl alcohols (e.g., 4-vinylbenzyl alcohol), and maleic anhydride.

[0116] The amount of the compound represented by formula (8) or formula (9) used may be adjusted according to the equivalent weight of the group at the molecular end of compound (A). For example, the amount of the compound represented by formula (8) or formula (9) used may be in the range of 2.0 to 2.5 moles per mole of compound (A).

[0117] The reaction conditions of the compound (A) and the compound represented by formula (8) or formula (9) are not particularly limited. The reaction temperature is preferably 0° C. or higher, 20° C. or higher, and preferably 100° C. or lower, 80° C. or lower. The reaction time is preferably 0.1 to 50 hours, more preferably 1 to 24 hours.

[0118] The reaction can be carried out in a solvent. The solvent is preferably one capable of dissolving the compound (A). Such a solvent is not particularly limited, but includes dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 1,3-dimethylimidazolidone (DMI), sulfolane, tetrahydrofuran (THF), and acetone. Among them, N-methyl-2-pyrrolidone (NMP) and 1,3-dimethylimidazolidone (DMI) are preferred. The amount of these solvents used is usually 10 to 1000 mL, preferably 50 to 400 mL, per 0.1 mole of the compound.

[0119] The above-mentioned manufacturing method usually produces a polymerization solution of fluorinated polyamide compound. The obtained polymerization solution of fluorinated polyamide compound may be used directly for various applications. After the reaction is completed, the reaction mixture is poured into a poor solvent such as methanol or water to separate the fluorinated polyamide compound, and then the fluorinated polyamide compound may be purified by reprecipitation to remove by-products, inorganic salts, etc., to obtain a fluorinated polyamide compound with high purity.

[0120] 4. Method for producing fluorinated polyimide compound The fluorinated polyimide compound of the present embodiment can be suitably produced by a production method in which a fluorinated polyamide compound of the present embodiment is obtained by the above-mentioned production method, and then the fluorinated polyamide compound is subjected to dehydration and cyclization.

[0121] When the fluorinated polyamide compound of this embodiment represented by formula (1) is dehydrated and cyclized, the fluorinated polyimide compound of this embodiment represented by formula (3) or formula (4) can be produced. In the case where the terminal portion of formula (1) has, for example, an ester bond, the terminal portion is not dehydrated and cyclized, and the fluorinated polyimide compound of this embodiment represented by formula (3) can be produced. In the case where the terminal portion of formula (1) has, for example, an amide bond, the terminal portion is dehydrated and cyclized, and the fluorinated polyimide compound of this embodiment represented by formula (4) can be produced. As described above, the crosslinking portion X' in formula (4) may have a different structure from the crosslinking portion X in formula (1), so for formality, the crosslinking portion in formula (4) is represented as X' instead of X.

[0122] The fluorinated polyimide compound of the present embodiment represented by formula (5) can be produced by dehydrating and cyclizing the fluorinated polyamide compound of the present embodiment represented by formula (2).

[0123] In addition, the fluorinated polyimide compound of this embodiment may be produced by modifying the terminals after the dehydration cyclization and adding X and Y. That is, when the reaction between the compound (A) and the compound represented by formula (8) or formula (9) is carried out under heating during the production of the fluorinated polyamide compound, a part or all of the compound (A) undergoes dehydration cyclization to form a compound (B) having a repeating unit represented by [] in formula (3), formula (4) or formula (5). X and Y are added to the residue at the molecular end of the compound (B), and as a result, the fluorinated polyimide compound of this embodiment may be obtained as a part or all of the product. For this reason, the present embodiment also includes mixtures and copolymers of fluorinated polyamide compounds and fluorinated polyimide compounds.

[0124] The compound (B) has a repeating unit structure represented by the following formula (B1) or (B2). [ka] (In formula (B1), m, n, ring A, ring B, R and L are as defined above.) [ka] (In formula (B2), m, n, ring A, ring B, R and L are as defined above.)

[0125] When a part or all of the compound (A) represented by formula (A1) undergoes cyclodehydration, a compound (B) having a repeating unit structure represented by formula (B1) is formed. When a part or all of the compound (A) represented by formula (A2) undergoes cyclodehydration, a compound (B) having a repeating unit structure represented by formula (B2) is formed.

[0126] The dehydration cyclization of the fluorinated polyamide compound can be carried out by heating the fluorinated polyamide compound. The heating temperature for the dehydration cyclization is preferably a temperature that does not allow the crosslinking reaction to proceed. The heating temperature for the dehydration cyclization is preferably 110°C or higher, 150°C or higher, and preferably 290°C or lower, 260°C or lower. The heating time is preferably 0.1 to 10 hours, more preferably 0.5 to 8 hours. The dehydration cyclization can be carried out in air, in a nitrogen or argon atmosphere, or under reduced pressure. The dehydration cyclization of the fluorinated polyamide compound may also be carried out by chemical imidization using a known and commonly used method.

[0127] The above-mentioned manufacturing method usually produces a solution of the fluorinated polyimide compound of the present embodiment. The obtained solution may be used as it is for various applications, or the obtained solution may be poured into a poor solvent such as methanol or water to separate the fluorinated polyimide compound, and then dried to produce a powder of the fluorinated polyimide compound, which may then be used. Alternatively, the solution of the fluorinated polyamide compound of the present embodiment may be applied to a substrate, dried, and then subjected to dehydration and cyclization under the same conditions as above to produce a film-like fluorinated polyimide compound of the present embodiment.

[0128] 5.Curable composition The curable composition of this embodiment may contain at least one of the fluorinated polyamide of this embodiment and the fluorinated polyimide of this embodiment, and a radical polymerization initiator. The curable composition of this embodiment may further contain a filler and / or a crosslinking agent. The curable composition of this embodiment contains a radical polymerization initiator, so that radical polymerization proceeds and the fluorinated polyamide compound of this embodiment and / or the fluorinated polyimide compound of this embodiment are crosslinked. This allows the cured product described below to be obtained. Each component of the curable composition of this embodiment will be described below.

[0129] 5-1. Radical polymerization initiator The radical polymerization initiator is not particularly limited, and examples thereof include a photoradical polymerization initiator and a thermal radical polymerization initiator. In the curable composition of the present embodiment, either a photoradical polymerization initiator or a thermal radical polymerization initiator may be used as the radical polymerization initiator. In addition, both a photoradical polymerization initiator and a thermal radical polymerization initiator may be used.

[0130] 5-1-1. Photoradical polymerization initiator The curable composition of this embodiment may contain a photoradical polymerization initiator. The photoradical polymerization initiator is a compound that generates radicals as active species by irradiation with light. By using the photoradical polymerization initiator, crosslinking proceeds in the exposed area, making the exposed area insoluble in the solvent, and crosslinking does not proceed in the unexposed area, making the exposed area soluble in the solvent. Therefore, a negative pattern can be formed in the obtained cured product. That is, the curable resin composition of this embodiment can also be used as a negative photosensitive resin composition by using a photoradical polymerization initiator as the radical polymerization initiator.

[0131] The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known compounds. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0132] Examples of the photoradical polymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes.

[0133] When a photoradical polymerization initiator is included, the content is preferably 0.1 parts by mass or more, 0.5 parts by mass or more, 1.0 parts by mass or more, 1.5 parts by mass or more, etc., when the total solid content of the fluorinated polyamide and fluorinated polyimide in the curable composition of this embodiment is 100 parts by mass. In addition, it is preferably 30 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, etc. The photoradical polymerization initiator may be included only one type, or may be included two or more types. When two or more types of photoradical polymerization initiators are included, the total is preferably within the above range.

[0134] 5-1-2. Thermal radical polymerization initiator The curable composition of the present embodiment may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction. By using the thermal radical polymerization initiator, the radical polymerization reaction proceeds upon heating, so that the crosslink density can be further improved. That is, the curable resin composition of the present embodiment can also be used as a thermosetting resin composition by using a thermal radical polymerization initiator as a radical polymerization initiator.

[0135] Specific examples of the thermal radical polymerization initiator include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and azo compounds.

[0136] When the thermal radical polymerization initiator is contained, the content is preferably 0.1 parts by mass or more, 5 parts by mass or more, etc., when the total solid content of the fluorinated polyamide and fluorinated polyimide in the curable composition of this embodiment is 100 parts by mass. Also, it is preferably 30 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, etc. The thermal radical polymerization initiator may be contained only one type, or may contain two or more types. When two or more types of thermal radical polymerization initiators are contained, the total is preferably within the above range.

[0137] Filler The curable composition of the present embodiment may contain a filler. As the filler, either an organic filler or an inorganic filler may be used. As the organic filler, for example, imide-based fillers having an imide structure such as polyimide, polyamideimide, and polyetherimide, and organic fillers made of engineering plastics such as polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyetherketone, and polyoxybenzoate may be used.

[0138] Examples of inorganic fillers include clay minerals such as talc, mica, sericite, and montmorillonite, metal oxides such as silica, alumina, and titanium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, fillers having a ferovskite crystal structure such as barium titanate and strontium titanate, boron nitride, aluminum borate, barium sulfate, and calcium carbonate. Among these, silica is preferred from the viewpoints of dielectric properties and thermal expansion, and alumina is preferred from the viewpoint of heat dissipation.

[0139] The above-mentioned fillers may be blended alone or in combination of two or more kinds.

[0140] When the above-mentioned filler is used, the content of the filler in the entire curable composition of the present embodiment is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. The content of the filler is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 70% by mass or less. If the content of the filler is within the above range, the dielectric tangent of the obtained cured product is further reduced, and the mechanical strength is also excellent.

[0141] 5-3. Crosslinking agent The curable composition of this embodiment may contain a crosslinking agent. The crosslinking agent is a compound that is added to promote crosslinking. Examples of the crosslinking agent include oximes such as p-quinone dioxime and p,p'-dibenzoylquinone dioxime; acrylates or methacrylates such as ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, cyclohexyl methacrylate, acrylic acid / zinc oxide mixture, allyl methacrylate, and trimethacryl isocyanurate (TMIC); vinyl monomers such as divinylbenzene, vinyl toluene, and vinyl pyridine; allyl compounds such as hexamethylene diallyl nadiimide, diaryl itaconate, diallyl phthalate, diallyl isophthalate, diallyl monoglycidyl isocyanurate, triallyl cyanurate, and triallyl isocyanurate (TAIC); and maleimide compounds such as N,N'-m-phenylene bismaleimide and N,N'-(4,4'-methylene diphenylene) dimaleimide. These crosslinking agents may be used alone or in combination of two or more.

[0142] Among the crosslinking agents exemplified above, TMIC and TAIC have excellent crosslinking properties due to their trifunctionality, and by incorporating these, crosslinking is further promoted, making it possible to obtain a cured product with excellent strength. TAIC is also preferred in that it has low toxicity to the human body.

[0143] When a crosslinking agent is contained, the content of the crosslinking agent is preferably 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, and preferably 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, when the total solid content of the fluorinated polyamide compound and the fluorinated polyimide compound in the curable composition of the present embodiment is taken as 100 parts by mass.

[0144] Furthermore, the curable composition of the present embodiment may further contain other additives, such as a plasticizer and a colorant, as necessary.

[0145] 6. Manufacturing method of the cured product The cured product of this embodiment can be produced from the curable composition described above. That is, the radical polymerization initiator generates radicals by irradiation with light or heating, and the crosslinking sites located at the respective ends of the molecules of the fluorinated polyamide compound or fluorinated polyimide compound react with each other to advance crosslinking, thereby forming the cured product of this embodiment.

[0146] For crosslinking, a fluorinated polyamide compound, a fluorinated polyimide compound, or a mixture of a fluorinated polyamide compound and a fluorinated polyimide compound can be used. The fluorinated polyamide compound or the fluorinated polyamide compound in the mixture is crosslinked and cyclodehydrated to obtain a cured product having the same structure as the cured product obtained by crosslinking the fluorinated polyimide compound. It is not necessary to crosslink and cyclodehydrate at the same time, and they may be performed separately.

[0147] The fluorinated polyamide compound of this embodiment is a crosslinkable fluorinated polyamide compound, and the fluorinated polyimide compound of this embodiment is a crosslinkable fluorinated polyimide compound. Therefore, when a photoradical polymerization initiator is used as the radical polymerization initiator, crosslinking can be performed by irradiating the curable composition of this embodiment with light. In addition, when a thermal radical polymerization initiator is used as the radical polymerization initiator, crosslinking can be performed by heating the curable composition of this embodiment.

[0148] When a thermal radical polymerization initiator is used as the radical polymerization initiator, the heating temperature for crosslinking is preferably 200°C or higher, more preferably 220°C or higher, and 350°C or lower, more preferably 300°C or lower. The heating time is preferably 0.1 to 5 hours, more preferably 0.5 to 4 hours. During crosslinking, the fluorinated polyamide compound or the fluorinated polyimide compound may be heated so that the temperature of the fluorinated polyamide compound or the fluorinated polyimide compound is slowly increased. The temperature increase rate may be 1 to 10°C / min.

[0149] Before crosslinking, the fluorinated polyamide compound or the fluorinated polyimide compound may be molded into a desired shape. The fluorinated polyamide compound or the fluorinated polyimide compound may be molded by heating and melting it, or a solution containing the fluorinated polyamide compound or the fluorinated polyimide compound may be prepared, and a substrate may be impregnated with the obtained solution or the obtained solution may be applied to a substrate to be molded.

[0150] Before crosslinking, a filler may be mixed into the curable composition containing the fluorinated polyamide compound and / or the fluorinated polyimide compound and the radical polymerization initiator. This allows a cured product containing the filler to be obtained. In addition, before crosslinking, a crosslinking agent may be mixed into the curable composition containing the fluorinated polyamide compound and / or the fluorinated polyimide compound and the radical polymerization initiator. This allows crosslinking to be further promoted and a cured product having excellent strength to be obtained. Furthermore, other additives, such as a plasticizer, a colorant, etc., may be mixed into the curable composition containing the fluorinated polyamide compound and / or the fluorinated polyimide compound and the radical polymerization initiator.

[0151] For mixing the fluorinated polyamide compound or fluorinated polyimide compound with the radical polymerization initiator, the filler, the crosslinking agent, other additives, etc., a typical polymer processing machine, for example, an open roll, a Banbury mixer, a kneader, an internal mixer, a roll mill, a bead mill, a ball mill, etc., can be used.

[0152] The cured product of the present embodiment achieves both low dielectric properties and solvent resistance due to the skeleton of the fluorinated polyamide compound or fluorinated polyimide compound and the crosslinked structure formed by crosslinking.

[0153] 7.Applications The cured product of this embodiment has excellent low dielectric properties and can therefore be suitably used as a low dielectric material for electronic parts, semiconductors, and electronic devices.

[0154] Specifically, the material can be used for semiconductor package wiring boards, flexible printed wiring boards, rigid printed wiring boards; TAB tapes, COF tapes, etc.; cover substrates for metal wiring, chip components such as IC chips, etc.; insulating films used in liquid crystal displays, organic electroluminescence displays, electronic paper, solar cells, etc.; base substrates, adhesive sheets, prepregs, primers, etc.

[0155] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0156] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to these examples.

[0157] The physical properties of each of the Synthesis Examples, Examples, and Comparative Examples were measured by the following methods. (1) Molecular weight measurement: Tosoh Corporation high-speed GPC system HLC-8220GPC (column: Tosoh TSKgel (α-M), column temperature: 45°C, detector: UV-8020, wavelength 254 nm, eluent: N-methyl-2-pyrrolidone (NMP) (containing 0.01 mol / L lithium bromide), calibration curve: standard polystyrene, column flow rate: 0.2 mL / min) (2) Infrared absorption spectrum (FT-IR): FT / IR-4200 manufactured by JASCO Corporation (3) Nuclear magnetic resonance spectrum (NMR): BRUKER AC400P (4) Measurement of weight loss temperature For each evaluation sample, measurements were performed using a TGA5500 manufactured by TA Instruments under conditions of a heating rate of 10°C / min, a starting temperature of 30°C, and an ending temperature of 600°C. The temperature at which the weight loss reached 5% by mass was recorded as the 5% weight loss temperature. (5) Glass transition temperature measurement: Each evaluation sample was measured using a DSC-Q100 manufactured by TA Instruments, Inc. by heating it to 300° C. at a heating rate of 10° C. / min, then cooling it to 20° C., and heating it again to 400° C. The glass transition temperature was evaluated from the measurement results of the second heating process. (6) Coefficient of linear thermal expansion (CTE) measurement: Each evaluation sample was cut into a strip of 3 mm width, and measured using a TMA-Q400 manufactured by TA Instruments, Inc., where the distance between the grippers was 16 mm and the temperature was raised to 150°C at a heating rate of 10°C / min, then the sample was cooled to -55°C and heated again to 400°C. The average CTE from 30°C to 150°C was evaluated from the measurement results of the second heating process. (7) Tensile test: Each evaluation sample was cut into a strip with a width of 5 mm, and measured at a gripping distance of 50 mm and a tensile speed of 10 mm / min using an EZ-SX made by Shimadzu Corporation. The elastic modulus was calculated from the average slope of the stress-strain curve obtained by the measurement in the stress range of 5 to 10 MPa. (8) Dielectric constant measurement: Each evaluation sample was cut into a size of 80 mm x 45 mm and measured by the SPDR (Split Post Dielectric Resonator) resonator method using a vector network analyzer E5071C manufactured by Keysight Technologies, LLC. The measurement was performed at a frequency of 10 GHz and a measurement temperature of 25°C, and the dielectric constant and dielectric loss tangent were calculated using a calculation program manufactured by QWED. (9) Solvent resistance test: Each evaluation sample is immersed in NMP, and after 5 hours, it is visually confirmed whether the cured product has dissolved.

[0158] <Synthesis Example 1> Synthesis of 4,4'-(1,6-perfluorohexylene)diphthalic anhydride (6PFDAH)

[0159] [ka]

[0160] In a recovery flask (100 mL), 4-iodo-O-xylene (10.0 g, 43 mmol), 1,6-diiodoperfluorohexane (13.6 g, 24 mmol), and DMSO (28 mL) were added and dissolved. Then, copper powder (13.9 g, 219 mmol) was added and reacted for 24 hours at 120 ° C under a nitrogen stream. After the reaction, it was cooled to room temperature, t-butyl methyl ether was added to dissolve the product, and the copper powder was removed by suction filtration. Distilled water was added to the filtrate, the organic layer was collected, and after dehydration with anhydrous sodium sulfate, t-butyl methyl ether was distilled off to obtain a white product (6PFBOX). This was recrystallized with methanol to obtain white needle-like crystals. The yield was 8.5 g, the yield was 77%, and the melting point was 84-85 ° C.

[0161] 1 H-NMR (CDCl 3 ,ppm):7.33(s,2H,ArH), 7.31(d,2H,ArH), 7.23(d,2H,ArH), 2.31(s,12H,CH 3 ) 13 C-NMR (CDCl 3 , ppm): 140.9, 137.1, 129.8, 127.8, 126.8, 124.4, 19.8 19 F-NMR (CDCl 3 ,ppm):-132.2, -122.7, -111.6 FT-IR (KBr, cm -1 ):2944(CH), 2924(CH), 1222(CF), 1130(CF) Elemental analysis (C 22 H 18 F 12): Calculated value C, 51.77%; H, 3.56% Actual value: C, 51.53%; H, 3.58%

[0162] In a 500 mL eggplant flask, 6PFBOX (4.0 g, 7.8 mmol), t-butyl alcohol (40 mL), and distilled water (160 mL) were placed and stirred. 4 (30.4g, 192mmol) was added at room temperature, and the mixture was reacted at 85°C for 1 hour and at 100°C for 48 hours. After the reaction, the mixture was cooled to room temperature, and a saturated aqueous solution of sodium hydrogen carbonate (8.1g, 96mmol) was added to the reaction solution and stirred for 30 minutes. The reaction solution was filtered through Celite, and concentrated hydrochloric acid was added to the filtrate to precipitate a white product. t-Butyl methyl ether (100mL) was added, and the mixture was stirred for 1 hour to dissolve the product in the organic layer, and the organic layer was collected. The organic layer was washed with saline until it became neutral. The organic layer was dehydrated with anhydrous sodium sulfate, and t-butyl methyl ether was distilled off to obtain a white product (6PFBPA). This was recrystallized with a mixed solvent of distilled water / acetone to obtain white needle-like crystals. The yield was 3.8g, the yield was 77%, and the melting point was 207-208°C.

[0163] 1 H-NMR (DMSO-d 6 ,ppm):13.6(br,4H,OH), 7.94-7.93(m,4H,ArH), 7.89(d,2H,ArH) 13 C-NMR (DMSO-d 6 ,ppm):168.0, 167.0, 137.6, 132.9, 129.7, 129.4, 129.3, 126.8 19 F-NMR (DMSO-d 6 ,ppm):-111.6,-122.7,-123.2 FT-IR (KBr, cm -1 ):3114(OH), 1736(C=O), 1222(CF), 1130(CF) Elemental analysis (C 22 H 10 O 8 F 12): Calculated value C, 41.92%; H, 1.60% Actual value: C, 41.72%; H, 1.78%

[0164] 6PFBPA (3.5g, 5.6mmol) and acetic anhydride (18mL) were placed in a recovery flask (500mL) and stirred at 140℃ under a nitrogen stream for 15 hours. After the reaction, the acetic anhydride was distilled off under reduced pressure to obtain a pale yellow product. This was recrystallized with a mixed solvent of dehydrated ethyl acetate and dehydrated hexane to obtain pale brown needle-like crystals, which were further purified by sublimation (185℃ / 0.2Torr) to obtain white powder crystals (6PFDAH). The yield was 1.9g, the yield was 58%, and the melting point was 190-191℃.

[0165] 1 H-NMR (CDCl 3 ,ppm):8.27(s,2H,ArH), 8.21(d,2H,ArH), 8.15(d,2H,ArH) 13 C-NMR (CDCl 3 ,ppm):161.4, 161.3, 134.8, 134.4, 132.4, 132.0, 126.4, 124.8 19 F-NMR (CDCl 3 , ppm): -112.1, -122.3, -122.5 FT-IR (KBr, cm -1 ):3140~3010(Ar-H), 1862(C=O), 1798(C=O), 1134(CF) Elemental analysis (C 22 H 6 O 6 F 12 ): Calculated value C, 44.46%; H, 1.02% Actual value: C, 44.28%; H, 1.16%

[0166] <Synthesis Example 2> Synthesis of fluorinated polyimide compound (6PFDAH-TFMB)

[0167] [ka]

[0168] TFMB (0.454 g, 1.42 mmol) and NMP (4 g) were placed in a 20 mL vial equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring. 6PFDAH (0.841 g, 1.42 mmol) was added to this solution, and dissolved by stirring at room temperature for 24 hours. After the reaction was completed, the solution was diluted with tetrahydrofuran (THF) to precipitate a fluorinated polyamide compound. The precipitated fluorinated polyamide compound was collected by suction filtration and dried under reduced pressure at room temperature for 12 hours. The crude yield was 85%. The dried fluorinated polyamide compound was dissolved in NMP (4 g), and the polymerization solution was applied to a copper foil using an applicator with a gap of 200 μm, dried at 90 ° C for 30 minutes, and then heated at 250 ° C for 1 hour in a nitrogen atmosphere to obtain a fluorinated polyimide compound (6PFDAH-TFMB). The obtained fluorinated polyimide compound was peeled off from the copper foil to obtain an evaluation sample of Synthesis Example 2.

[0169] <Synthesis Example 3> Synthesis of fluorinated polyimide compound (6FDA-ODA)

[0170] [ka]

[0171] A sample for evaluation in Synthesis Example 3 was obtained in the same manner as in Synthesis Example 2, except that 4,4'-diaminodiphenyl ether (ODA) (0.454 g, 1.42 mmol) was used instead of TFMB, and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) (0.841 g, 1.42 mmol) was used instead of 6PFDAH.

[0172] <Synthesis Example 4> Synthesis of fluorinated polyimide compound (6FDA-TFMB)

[0173] [ka]

[0174] A sample for evaluation in Synthesis Example 4 was obtained in the same manner as in Synthesis Example 2, except that 6FDA (0.841 g, 1.42 mmol) was used instead of 6PFDAH.

[0175] The physical properties of the compounds obtained in Synthesis Examples 2 to 4 are shown in the following Table 1. 6PFDAH-TFMB of Synthesis Example 2 exhibited a significantly lower dielectric tangent than other fluorine-containing polyimide compounds.

[0176] [Table 1]

[0177] <Experimental Example 1> Fluorinated polyamide compounds and fluorinated polyimide compounds (6PFDAH-TFMB-St)

[0178] [ka]

[0179] 2,2'-bis(trifluoromethyl)benzidine (TFMB) (0.802 g, 2.5 mmol) and ultra-dehydrated NMP (7 g) were placed in a 20 mL vial equipped with a stirrer and nitrogen inlet tube, and dissolved by stirring. 6PFDAH (1.56 g, 2.63 mmol) was added to this solution, and dissolved by stirring at room temperature for 1 hour. Next, 4-aminostyrene (0.030 g, 0.25 mmol) was added as a terminal monomer, and reacted at room temperature for 24 hours by stirring to obtain a polymerization solution of the fluorinated polyamide compound of Experimental Example 1, which is a precursor.

[0180] The physical properties of the resulting fluorinated polyamide compound are shown below. Number average molecular weight (Mn): 11,300 Weight average molecular weight (Mw): 39,324 Molecular weight distribution (Mw / Mn): 3.48

[0181] <Experimental Example 2> Fluorinated polyamide compounds and fluorinated polyimide compounds (6PFDAH-TFMB-Ph)

[0182] [ka]

[0183] A polymerization solution of a fluorinated amide compound of Experimental Example 2 having a phenyl group introduced at the end was obtained in the same manner as in Experimental Example 1, except that aniline (0.023 g, 0.25 mmol) was used as the terminal monomer.

[0184] The physical properties of the resulting fluorinated polyamide compound are shown below. Number average molecular weight (Mn): 9,100 Weight average molecular weight (Mw): 31,941 Molecular weight distribution (Mw / Mn): 3.51

[0185] <Example 1> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St)

[0186] 0.03 g of Perbutyl P40 (manufactured by NOF Corp.), a thermal radical polymerization initiator, was mixed and stirred into 3.02 g of the polymerization solution (solid content concentration 24 mass%) of the fluorinated polyamide compound (6PFDAH-TFMB-St) having a crosslinkable group obtained in Experimental Example 1 to obtain a curable composition containing the fluorinated polyamide compound. The curable composition was applied onto a copper foil using an applicator with a gap of 200 μm, dried at 90° C. for 30 minutes, and then heated at 250° C. for 1 hour in a nitrogen atmosphere to obtain a cured product of Example 1 that was dehydrated, cyclized, and crosslinked. The cured product was peeled off from the glass substrate to prepare an evaluation sample of Example 1.

[0187] <Comparative Example 1> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-Ph)

[0188] An evaluation sample for Comparative Example 1 was prepared in the same manner as in Example 1, except that a polymerization solution (solid content concentration: 24 mass%) of the fluorinated polyamide compound (6PFDAH-TFMB-Ph) having a phenyl group at the end of Experimental Example 2 was used.

[0189] <Comparative Example 2> Cured material from fluorinated polyamide compound (6PFDAH-TFMB)

[0190] In Comparative Example 2, the same evaluation sample as in Synthesis Example 2 was used.

[0191] The physical properties of the cured products obtained in Example 1 and Comparative Examples 1 and 2 are shown in Table 2 below. It was shown that the cured product of Example 1 maintained the excellent low dielectric tangent properties of 6PFDAH-TFMB while also exhibiting excellent solvent resistance.

[0192] [Table 2]

[0193] <Example 2> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 20.4%, crosslinker weight ratio: 0%)

[0194] An evaluation sample for Example 2 was prepared in the same manner as in Example 1, except that a curable composition was used in which 1.61 g of a fluorinated polyamide solution having a solid content of 24 wt%, obtained by dissolving the fluorinated polyamide compound powder of Experimental Example 1 in cyclohexanone, 0.15 g of a cyclohexanone slurry having a solid content of 70 wt% in which a spherical silica filler {SC2050-HNF (manufactured by Admatechs Co., Ltd.)} was dispersed, and 0.04 g of Perbutyl P40 (manufactured by NOF Corporation) were mixed and stirred, and the applicator gap was adjusted so that the film thickness after drying was 50 μm.

[0195] <Example 3> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 38.5%, crosslinker weight ratio: 0%)

[0196] An evaluation sample of Example 3 was prepared in the same manner as Example 2, except that the blending amounts of each component were set to the values ​​shown in Table 3.

[0197] <Example 4> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 56.9%, crosslinker weight ratio: 0%)

[0198] An evaluation sample of Example 4 was prepared in the same manner as in Example 2, except that the blending amounts of each component were set to the values ​​shown in Table 3.

[0199] <Example 5> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 78.8%, crosslinker weight ratio: 0%)

[0200] An evaluation sample of Example 5 was prepared in the same manner as Example 2, except that the blending amounts of each component were set to the values ​​shown in Table 3.

[0201] The physical properties of each of the cured films of Examples 2 to 5 are shown in Table 3 below. The blend amounts in Table 3 represent solid content amounts.

[0202] [Table 3]

[0203] <Example 6> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 67.0%, crosslinker weight ratio: 6.0%)

[0204] An evaluation sample of Example 6 was prepared in the same manner as in Example 2, except that {TAIC (manufactured by Nippon Kasei Co., Ltd.)} was used as the crosslinking agent and the amounts of each component were set to the values ​​shown in Table 4.

[0205] <Example 7> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 66.4%, crosslinker weight ratio: 11.2%)

[0206] An evaluation sample of Example 7 was prepared in the same manner as in Example 6, except that the blending amounts of each component were set to the values ​​shown in Table 4.

[0207] <Example 8> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 67.2%, crosslinker weight ratio: 16.0%)

[0208] An evaluation sample of Example 8 was prepared in the same manner as in Example 6, except that the blending amounts of each component were set to the values ​​shown in Table 4.

[0209] <Example 9> Cured material from fluorinated polyimide compound (6PFDAH-TFMB-St) (Filler weight ratio: 68.1%, crosslinker weight ratio: 0.0%)

[0210] An evaluation sample of Example 9 was prepared in the same manner as in Example 6, except that no crosslinking agent was added and the amounts of each component were set to the values ​​shown in Table 4.

[0211] The physical properties of each of the cured films of Examples 6 to 9 are shown in Table 4 below.

[0212] [Table 4] [Industrial Applicability]

[0213] The fluorinated polyamide compound and fluorinated polyimide compound of the present invention can give a cured product that has both low dielectric tangent properties and solvent resistance, and can therefore be suitably used as a low dielectric material for materials for electronic components, semiconductors, and electronic devices.

Claims

1. A fluorinated polyamide compound represented by the following chemical formula (1) or the following chemical formula (2): 【Chemistry 1】 (In formula (1), m represents the average degree of polymerization of the repeating unit represented by [ ], n represents an integer of 1 to 8, ring A and ring B each independently represent a group having a hydrocarbon ring having or without a substituent, R each independently represent a hydrogen atom, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, R １ each independently represents a hydroxyl group, a linear or branched alkoxy group which may have a substituent, an aromatic oxy group which may have a substituent, or a halogen atom; L represents a linking group; X independently represents a monovalent organic group having an unsaturated carbon bond; R ２ is the R １ or any of the groups represented by X above. 【Chemistry 2】 (In formula (2), m represents the average degree of polymerization of the repeating unit represented by [ ], Y represents independently a monovalent organic group having an unsaturated carbon bond, n represents a ring A, a ring B, R, L and R １ is as stated above.)

2. 2. The fluorinated polyamide compound according to claim 1, wherein, in the chemical formula (1) or the chemical formula (2), the X and the Y are monovalent organic groups having a styryl group.

3. A fluorinated polyimide compound represented by the following chemical formula (3), the following chemical formula (4), or the following chemical formula (5). 【Chemistry 3】 (In formula (3), m is the average degree of polymerization of the repeating unit represented by [ ], n is an integer of 1 to 8, ring A and ring B are independently a group having a hydrocarbon ring which may or may not have a substituent, R is independently a hydrogen atom, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, L is a linking group, X is independently a monovalent organic group having an unsaturated carbon bond, R ２ each independently represents a hydroxyl group, a linear or branched alkoxy group which may have a substituent, an aromatic oxy group which may have a substituent, a halogen atom, or a group represented by X. 【Chemistry 4】 (In formula (4), X' is independently a monovalent organic group having an unsaturated carbon bond, and m, n, ring A, ring B, R and L are as defined above.) 【Chemistry 5】 (In formula (5), m is the average degree of polymerization of the repeating units represented by [ ], Y is independently a monovalent organic group having an unsaturated carbon bond, and n, ring A, ring B, R and L are as defined above.)

4. 4. The fluorinated polyimide compound according to claim 3, wherein in the chemical formula (3), the chemical formula (4), or the chemical formula (5), the X, the X', and the Y are monovalent organic groups having a styryl group.

5. At least one of the fluorinated polyamide compound according to claim 1 or 2 and the fluorinated polyimide compound according to claim 3 or 4, and a radical polymerization initiator.

6. The curable composition of claim 5 further comprising a filler.

7. The curable composition according to claim 6 , wherein the content of the filler in the entire curable composition is 10 mass % or more.

8. The curable composition of claim 5 further comprising a crosslinker.

9. A cured product formed from the curable composition according to claim 5 .

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