Resin composition and cured product

Abstract

To provide a resin composition that excels in low dielectric loss tangent characteristics, a resin composition capable of yielding a cured product that excels in low dielectric loss tangent characteristics, and a cured product formed from the resin composition.SOLUTION: The present invention provides a fluorinated polyamide compound having a repeating structure represented by formula (1), a resin composition containing at least one of the fluorinated polyamide compound and a corresponding fluorinated polyimide derivative, and a cured product formed from the resin composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a resin composition and a cured product. [Background technology]

[0002] Patent Document 1 describes a fluorinated nitrogen-containing heterocycle-containing compound having a repeating structure 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 density of semiconductors, polyimide compounds are required to have low dielectric properties.

[0005] Therefore, the present disclosure provides a resin composition having excellent low dielectric tangent characteristics, a resin composition capable of giving a cured product having excellent low dielectric tangent characteristics, and a cured product formed from the resin composition. [Means for solving the problem]

[0006] One embodiment of the present disclosure is a resin composition comprising at least one of a fluorinated polyamide compound having a repeating structure represented by the following chemical formula (1) and a fluorinated polyimide compound having a repeating structure represented by the following chemical formula (2).

[0007] [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, and L represents a linking group.

[0008] [ka] (In formula (2), m, n, ring A, ring B, R and L are as defined above.)

[0009] The resin composition of the present disclosure preferably further contains a radical polymerization initiator, an acid generator, or a base generator.

[0010] The resin composition of the present disclosure preferably further contains a crosslinking agent.

[0011] The resin composition of the present disclosure preferably further contains a filler.

[0012] In the resin composition of the present disclosure, the content of the filler relative to the total solid content of the resin composition is preferably 10 mass % or more.

[0013] Yet another aspect of the present disclosure is a cured product formed from the resin composition. Effect of the Invention

[0014] According to the present disclosure, it is possible to provide a resin composition having excellent low dielectric tangent characteristics, a resin composition capable of giving a cured product having excellent low dielectric tangent characteristics, and a cured product formed from the resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] 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.

[0016] When a compound is described, all its isomers are also described.

[0017] 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.

[0018] 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.

[0019] The term "aromatic" is not particularly limited, and unless otherwise specified, also includes heterocycles.

[0020] Specific embodiments of the present disclosure will be described in detail below, but the present disclosure is not limited to the following embodiments.

[0021] 1. Fluorinated polyamide compounds The fluorinated polyamide compound of this embodiment has a repeating structure represented by formula (1).

[0022] [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, and L represents a linking group.

[0023] The fluorinated polyamide compound of this embodiment contains a repeating structure represented by the formula (1), in which ring A is a linear perfluoroalkylene group (-(CF 2 ) n -) is bonded. Therefore, the fluorinated polyimide compound derived from the fluorinated polyamide of formula (1) 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.

[0024] 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.

[0025] 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.

[0026] n represents an integer of 1 to 8. n is preferably an integer of 4 to 8, more preferably an integer of 4 to 6, and further preferably 4 or 6, since the dielectric constant and dielectric dissipation factor of the fluorinated polyimide compound derived from the fluorinated polyamide compound can be further reduced.

[0027] 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.

[0028] 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 A is preferably 6 to 20, and more preferably 6 to 15.

[0029] 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.

[0030] R 1are 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.

[0031] R 1 The 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.

[0032] 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.

[0033] 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.

[0034] R 1 may independently be a hydroxyl group, an unsubstituted phenoxy group, a methoxy group, an ethoxy group, a chlorine atom, or a compound represented by the following formula: [ka]

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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 is, for example, 1 to 8.

[0039] The fluorinated alkylene group is more preferably a perfluoroalkylene group represented by the following formula, since this makes it 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.)

[0040] n1 may be an integer of 4 to 8, an integer of 4 to 6, and more preferably 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.

[0041] The repeating structure represented by formula (1) is preferably a repeating structure represented by formula (1-1). [ka] (In formula (1-1), m, n, L and R 1 is as described above.)

[0042] Examples of the fluorinated polyamide compound include compounds represented by the following formula: [ka] (Wherein, m, n, L and R 1 is as described above. 2 each independently represents hydrogen or a monovalent organic group.

[0043] R 2 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.

[0044] Specific examples of the monovalent organic group include -CH 3 , -C 2 H 5 , -C 3 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 , -CH2 C 6 H 5-k (CF 3 ) k (k is an integer from 1 to 5) 3 aliphatic acyl groups such as acetyl group and pivaloyl group; aromatic acyl groups such as benzoyl group and methylbenzoyl group; fluorinated acetyl groups such as fluoroacetyl group and trifluoroacetyl group; and fluorobenzoyl group and trifluoromethylbenzoyl group.

[0045] R 2 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.

[0046] The number average molecular weight (Mn) of the fluorinated polyamide compound of the present embodiment is preferably 2,000 or more, 5,000 or more, 10,000 or more, and is preferably 1,000,000 or less, 500,000 or less, 100,000 or less.

[0047] The molecular weight distribution (Mw / Mn) of the fluorinated polyamide compound of the present embodiment is preferably 1.5 or more, more preferably 2 or more, and is preferably 5 or less, more preferably 4 or less.

[0048] The fluorinated polyamide compound of the present embodiment can be suitably used as a precursor of a fluorinated polyimide compound having a repeating structure represented by the formula (2) described below. In addition, the fluorinated polyamide compound of the present embodiment can be crosslinked to obtain a cured product described below.

[0049] 2. Fluorinated polyimide compounds The fluorinated polyimide compound of the present embodiment has a repeating structure represented by formula (2).

[0050] [ka] (In formula (2), m, n, ring A, ring B, R and L are the same as those in formula (1).)

[0051] The fluorinated polyimide compound of this embodiment has a repeating structure represented by the formula (2), in which ring A is a linear perfluoroalkylene group (-(CF 2 ) n -) is bonded. Therefore, the fluorinated polyimide compound of formula (2) has a lower dielectric tangent than conventional ones, and exhibits excellent low dielectric properties. In addition, the fluorinated polyimide compound of this embodiment exhibits excellent solubility in organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide.

[0052] In formula (2), m, n, ring A, ring B, R, and L are the same as those in formula (1), and by adopting a preferred structure similar to that in formula (1), the dielectric constant and dielectric tangent of the fluorinated polyimide compound can be further reduced.

[0053] The repeating structure represented by formula (2) is preferably a repeating structure represented by formula (2-1).

[0054] [ka] (In formula (2-1), m, n, and L are as defined above.)

[0055] The fluorinated polyimide compound may, for example, be a compound represented by the following formula:

[0056] [ka] (In the formula, m, n, L, R 1 and R 2 is as described above.)

[0057] The dielectric loss tangent (Df) at 10 GHz of the fluorinated polyimide compound of the present embodiment is preferably 0.005 or less, and more preferably 0.0045 or less.

[0058] The glass transition temperature of the fluorinated polyimide compound of the present embodiment is preferably 50° C. or more, 100° C. or more, 150° C. or more, or 200° C. or more, etc. Also, it is preferably 400° C. or less, 350° C. or less, 300° C. or less, or 260° C. or less, etc. The glass transition temperature is a value measured by differential scanning calorimetry (DSC).

[0059] The number average molecular weight (Mn) of the fluorinated polyimide compound of the present embodiment is preferably 2,000 or more, 5,000 or more, 10,000 or more, and is preferably 1,000,000 or less, 500,000 or less, 100,000 or less.

[0060] The molecular weight distribution (Mw / Mn) of the fluorinated polyimide compound of the present embodiment is preferably 1.5 or more, more preferably 2 or more, and is preferably 5 or less, more preferably 4 or less.

[0061] 3. Method for producing fluorinated polyamide compound The fluorinated polyamide compound of this embodiment can be suitably produced by polymerizing a compound represented by formula (3) and a compound represented by formula (4).

[0062] [ka] (In formula (3), n, ring A, R and R 1 In formula (4), 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.)

[0063] [ka] (In formula (4), rings B, L and R2 is as mentioned above.)

[0064] The compound represented by formula (3) is preferably a compound represented by formula (3-1).

[0065] [ka] (In formula (3-1), n ​​and R 1 In formula (3-1), 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.)

[0066] The compound represented by formula (4) is preferably a compound represented by formula (4-1).

[0067] [ka] (In formula (4-1), L and R 2 is as mentioned above.)

[0068] The polymerization of the compound represented by formula (3) and the compound represented by formula (4) can be carried out in a solvent. The solvent is preferably a good solvent for the fluorinated polyimide compound obtained by polymerizing the compound represented by formula (3) and the compound represented by formula (4), in addition to being substantially unreactive with the compound represented by formula (3) and the compound represented by formula (4) and having the property of dissolving the compound represented by formula (3) and the compound represented by formula (4) well. 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 (3) or the compound represented by formula (4).

[0069] 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. As the additive, lithium chloride is particularly preferred. 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.

[0070] The polymerization can be carried out, for example, by dissolving either the compound represented by formula (3) or the compound represented by formula (4) 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 20°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.

[0071] The average degree of polymerization m of the repeating unit represented by [ ] in formula (1) can be adjusted by changing the molar ratio of the compounds represented by formula (3) and formula (4) used in polymerization, the concentration of the polymerization solution, the polymerization temperature, the polymerization time, etc.

[0072] The molecular chain terminal of the compound represented by formula (1) has a residue of the compound represented by formula (3) or a residue of the compound represented by formula (4). The molecular chain terminal of the compound represented by formula (1) can be adjusted by controlling the molar ratio of the compound represented by formula (3) to the compound represented by formula (4). After polymerization, a crosslinking site such as a hydrocarbon group having an unsaturated carbon bond may be introduced by modifying a part of the compound represented by formula (1) or by introducing a terminal group into the compound represented by formula (1).

[0073] 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. The obtained solution of fluorinated polyamide compound may be poured into poor solvent such as methanol or water to separate fluorinated polyamide compound, and then purified by reprecipitation to remove by-products, inorganic salts, etc., to obtain a fluorinated polyamide compound with high purity.

[0074] 4. Method for producing fluorinated polyimide compound The fluorinated polyimide compound of this embodiment can be suitably produced by obtaining a fluorinated polyamide compound by the above-mentioned production method, and then dehydrating and cyclizing the fluorinated polyamide compound. When producing a fluorinated polyamide compound, if the polymerization of the compound represented by formula (3) and the compound represented by formula (4) is carried out under heating, a part or all of the compound is dehydrated and cyclized to form a compound having a repeating structure represented by [] in formula (2), and as a result, the fluorinated polyimide compound of this embodiment may be obtained as a part or all of the product. That is, this embodiment also includes a mixture or copolymer of a fluorinated polyamide compound and a fluorinated polyimide compound.

[0075] The dehydration and cyclization of the fluorinated polyamide compound can be carried out by heating the fluorinated polyamide compound. The heating temperature for the dehydration and cyclization is preferably 110°C or higher, 150°C or higher, and preferably 450°C or lower, 350°C or lower. The heating time is preferably 0.1 to 10 hours, more preferably 0.5 to 8 hours. The dehydration and cyclization can be carried out in air, in a nitrogen or argon atmosphere, or under reduced pressure. The dehydration and cyclization of the fluorinated polyamide compound may also be carried out by chemical imidization using a known and commonly used method.

[0076] The above-mentioned production method usually produces a solution of the fluorinated polyimide compound of the present invention. 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.

[0077] 5.Resin composition The resin composition of this embodiment preferably contains at least one of the fluorinated polyamide compound of this embodiment and the fluorinated polyimide compound of this embodiment. The resin composition of this embodiment may further contain a radical polymerization initiator, an acid generator, or a base generator. The resin composition of this embodiment may further contain a crosslinking agent. The resin composition of this embodiment may further contain a filler. The resin composition of this embodiment may further contain other additives.

[0078] The resin composition of this embodiment is obtained by mixing the fluorinated polyamide compound or fluorinated polyimide compound with other components (any components selected from radical polymerization initiators, acid generators, base generators, crosslinking agents, fillers, other additives, etc.) For mixing, a typical polymer processing machine such as a roll mill, a ball mill, a bead mill, an open roll, a Banbury mixer, a kneader, or an internal mixer can be used.

[0079] In the resin composition of the present embodiment, the fluorinated polyamide compound and / or the fluorinated polyimide compound of the present embodiment are crosslinked to obtain a cured product described below. Each component of the resin composition of the present embodiment will be described below.

[0080] 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 resin 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.

[0081] 5-1-1. Photoradical polymerization initiator The resin 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. For example, when the fluorinated polyamide and / or the fluorinated polyimide of this embodiment has a crosslinking site having an unsaturated carbon bond {e.g., a styryl group, an alkenyl group (vinyl group, allyl group, etc.), an acryloyl group, a methacryloyl group, an alkynyl group}, etc., by using a photoradical polymerization initiator, crosslinking proceeds in the exposed area and the area becomes insoluble, and crosslinking does not proceed in the unexposed area and the area becomes soluble. Therefore, a negative pattern can be formed in the obtained cured product. That is, the resin composition of this embodiment can also be used as a negative photosensitive resin composition by using a photoradical polymerization initiator as a radical polymerization initiator.

[0082] 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.

[0083] 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.

[0084] 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 compound and the fluorinated polyimide compound in the resin 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.

[0085] 5-1-2. Thermal radical polymerization initiator The resin 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. For example, when the fluorinated polyamide and / or the fluorinated polyimide of the present embodiment has a crosslinking site having an unsaturated carbon bond, the radical polymerization reaction proceeds upon heating by using a thermal radical polymerization initiator, and a cured product can be obtained. That is, the resin composition of the present embodiment can also be used as a thermosetting resin composition by using a thermal radical polymerization initiator as the radical polymerization initiator.

[0086] 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.

[0087] 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 compound and the fluorinated polyimide compound in the resin 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.

[0088] 5-2. Acid generator The resin composition of the present embodiment may contain an acid generator. The acid generator is not particularly limited, and examples thereof include a photoacid generator and a thermal acid generator.

[0089] 5-2-1. Photoacid generator A photoacid generator is a compound that generates an acid when irradiated with light such as ultraviolet light or visible light. Examples of photoacid generators include naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxyimide sulfonates, aromatic sulfamides, and benzoquinone diazosulfonic acid esters.

[0090] When the resin composition of the present embodiment contains a photoacid generator that functions as a dissolution inhibitor, such as a naphthoquinone diazide compound, the resin composition is insoluble in a solvent in the unexposed area, while being soluble in a solvent in the exposed area, and can therefore be used as a positive-type photosensitive resin composition. In addition, when the fluorinated polyamide and / or fluorinated polyimide of the present embodiment has an acid crosslinkable group (e.g., an epoxy group, a methylol group, an alkoxymethyl group, etc.), or when the resin composition of the present embodiment contains a crosslinking agent described later, the resin composition can also be used as a negative-type photosensitive resin composition by containing a photoacid generator.

[0091] When a photoacid generator is included, the content is preferably 0.1 parts by mass or more, 1 part by mass or more, etc., when the total solid content of the fluorinated polyamide compound and the fluorinated polyimide compound in the resin composition of this embodiment is 100 parts by mass. Also, it is preferably 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, etc. The photoacid generator may be included in only one type, or may be included in two or more types. When two or more types of photoacid generators are included, the total is preferably within the above range.

[0092] 5-2-2. Thermal acid generator The thermal acid generator is a compound that generates an acid by heating. Examples of the thermal acid generator include sulfonate compounds, sulfonimide compounds, sulfonium salts, 2-sulfobenzoic anhydride, p-toluenesulfonic anhydride, benzothiazolium salts, ammonium salts, phosphonium salts, and sulfonate salts. When the fluorinated polyamide and / or the fluorinated polyimide of the present embodiment have an acid crosslinking group, or when the resin composition of the present embodiment contains a crosslinking agent described later, the composition can also be used as a thermosetting resin composition by containing a thermal acid generator.

[0093] When a thermal acid generator is included, the content is preferably 0.1 parts by mass or more, 1 part by mass or more, etc., when the total solid content of the fluorinated polyamide compound and the fluorinated polyimide compound in the resin composition of this embodiment is 100 parts by mass. Also, it is preferably 50 parts by mass or less, 30 parts by mass or less, etc. The thermal acid generator may be included in only one type, or may be included in two or more types. When two or more types of thermal acid generators are included, the total is preferably within the above range.

[0094] 5-3. Base generator The resin composition of the present embodiment may contain a base generator. The base generator is not particularly limited, and examples thereof include a photobase generator and a thermal base generator. When the resin composition of the present embodiment contains a base generator, the fluorinated polyamide compound or the fluorinated polyimide compound preferably has a base-sensitive functional group.

[0095] 5-3-1. Photobase generator A photobase generator is a compound that generates a base by irradiation with light such as ultraviolet light or visible light. The photobase generator may be an ionic photobase generator or a nonionic photobase generator. Examples of ionic photobase generators include salts of aromatic component-containing carboxylic acids and tertiary amines, and ionic PBGs WPBG-082, WPBG-167, WPBG-168, WPBG-266, and WPBG-300 manufactured by Wako Pure Chemical Industries, Ltd. Examples of nonionic photobase generators include α-aminoacetophenone compounds, oxime ester compounds, and compounds having substituents such as N-formyl aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, and alkoxybenzyl carbamate groups. When the fluorinated polyamide and / or the fluorinated polyimide of the present embodiment has a base crosslinkable group (e.g., an epoxy group, etc.), or when the resin composition of the present embodiment contains a crosslinking agent described later, the resin composition can also be used as a negative-type photosensitive resin composition by including a photobase generator.

[0096] When a photobase generator is included, the content is preferably 0.1 parts by mass or more, 1 part by mass or more, etc., when the total solid content of the fluorinated polyamide compound and the fluorinated polyimide compound in the resin composition of this embodiment is 100 parts by mass. Also, it is preferably 50 parts by mass or less, 30 parts by mass or less, etc. The photobase generator may contain only one type, or may contain two or more types. When two or more types of photobase generators are contained, the total is preferably within the above range.

[0097] 5-3-2. Thermal base generator The thermal base generator is a compound that generates a base upon heating. Examples of the thermal base generator include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or a salt thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate salt, formate salt, tetraphenylborate salt, etc.); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or a salt thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate salt, formate salt, tetraphenylborate salt, etc.); tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and N,N-dimethylcyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphines such as phosphoric acid esters and triphenylphosphine; phosphonium compounds such as tetraphenylphosphonium tetra(p-tolyl)borate; organic metal salts such as zinc octylate and tin octylate; and metal chelates. When the fluorinated polyamide and / or the fluorinated polyimide of the present embodiment has a base crosslinkable group, or when the resin composition of the present embodiment contains a crosslinking agent described later, it can also be used as a thermosetting resin composition by including a thermal base generator.

[0098] When the thermal base generator is contained, the content is preferably 0.1 parts by mass or more, 1 part by mass or more, etc., when the total solid content of the fluorinated polyamide compound and the fluorinated polyimide compound in the resin composition of this embodiment is 100 parts by mass. Also, it is preferably 50 parts by mass or less, 30 parts by mass or less, etc. The thermal base generator may contain only one type, or may contain two or more types. When two or more types of thermal base generators are contained, the total is preferably within the above range.

[0099] 5-4. Crosslinking agent The resin composition of the present embodiment may contain a crosslinking agent. The crosslinking agent is an agent that can be crosslinked or polymerized by heating or the action of an acid, a base, or a radical. By using the crosslinking agent, the crosslinking of the fluorinated polyamide compound and / or the fluorinated polyimide compound of the present embodiment can be promoted to obtain a cured product. When the resin composition of the present embodiment contains a crosslinking agent, the above-mentioned acid generator or base generator may be contained from the viewpoint of improving reactivity.

[0100] The crosslinking agent is not particularly limited, and a known crosslinking agent may be used. The crosslinking agent has two or more crosslinkable groups in one molecule. For example, a crosslinking agent having an unsaturated carbon bond, a crosslinking agent having a phenolic hydroxyl group, a melamine-based crosslinking agent, a crosslinking agent having a cyclic ether group such as an epoxy group or a cyclic thioether group such as an episulfide group, a crosslinking agent having an alcoholic hydroxyl group in which a hydroxyl group is bonded to an alkylene group having 1 to 12 carbon atoms such as a methylol group, a compound having an ether bond such as an alkoxymethyl group, a crosslinking agent having a triazine ring structure, a urea-based crosslinking agent, etc. are listed. Among them, a crosslinking agent having an unsaturated carbon bond, a crosslinking agent having an epoxy group, and a crosslinking agent having a methylol group are preferable.

[0101] When a crosslinking agent is included, the content of the crosslinking agent is preferably 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 compound and the fluorinated polyimide compound in the resin composition of this embodiment is 100 parts by mass. Also, it is preferably 60 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, etc. The crosslinking agent may be contained only one type, or may be contained two or more types. When two or more types of crosslinking agents are contained, the total is preferably within the above range.

[0102] The crosslinking agent may be used in combination with one or more selected from the radical polymerization initiator, the acid generator, and the base generator described above.

[0103] Filler The resin composition of the present embodiment may contain a filler. When the resin composition of the present embodiment contains a filler, the filler can impart various properties, such as thermal properties, dielectric properties, mechanical properties, conductive properties, and heat dissipation properties, to the resin composition. 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 can be used.

[0104] 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 viewpoint of dielectric properties and thermal expansion, and alumina is preferred from the viewpoint of heat dissipation. The shape of the inorganic filler includes spherical, needle-like, plate-like, scaly, hollow, amorphous, hexagonal, cubic, and flaky shapes, and the like, with spherical being preferred from the viewpoint of high filling properties.

[0105] The above-mentioned fillers may be blended alone or in combination of two or more kinds.

[0106] When the above-mentioned filler is used, the content of the filler relative to the total solid content of the resin 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, a cured product having a higher mechanical strength can be obtained while further reducing the dielectric tangent.

[0107] 5-6. Other additives Furthermore, the resin composition of the present embodiment may further contain other additives, such as an organic solvent, a plasticizer, a colorant, and the like, as necessary.

[0108] 5-6-1. Organic solvents The organic solvent is not particularly limited, and known organic solvents can be used. For example, 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), acetone, etc. are mentioned. Among them, N-methyl-2-pyrrolidone (NMP), 1,3-dimethylimidazolidone (DMI), cyclohexanone, etc. are mentioned.

[0109] 6. Manufacturing method of the cured product The cured product of this embodiment can be formed by applying and drying the above-mentioned resin composition, followed by heating, etc. When the resin composition of this embodiment contains a fluorinated polyamide compound, the crosslinking and cyclodehydration are simultaneously carried out to obtain a cured product having the same structure as the cured product obtained from the fluorinated polyimide compound. Crosslinking and cyclodehydration do not need to be carried out simultaneously, and may be carried out separately.

[0110] When the resin composition of the present embodiment contains a crosslinking agent, crosslinking proceeds via the crosslinking agent to form the cured product of the present embodiment.

[0111] When the resin composition of the present embodiment contains a radical polymerization initiator, an acid generator, or a base generator, the crosslinking sites of the fluorinated polyamide compound or the fluorinated polyimide compound react with each other by irradiation with light or heating, and crosslinking proceeds to form the cured product of the present embodiment.When the resin composition of the present embodiment contains a crosslinking agent, the fluorinated polyamide compound or the fluorinated polyimide compound reacts with the crosslinking agent, and crosslinking proceeds to form the cured product of the present embodiment.

[0112] When a photoradical polymerization initiator, a photoacid generator, or a photobase generator is used, the formation of a cured product can be promoted by irradiating the resin composition with light. When a thermal radical polymerization initiator, a thermal acid generator, or a thermal base generator is used, the formation of a cured product can be promoted by heating the resin composition.

[0113] The heating temperature is preferably 180°C or more, 200°C or more, and 550°C or less, 400°C or less. The heating time is preferably 0.1 to 5 hours, more preferably 0.5 to 4 hours. At this time, the fluorinated polyamide compound or the fluorinated polyimide compound may be heated so as to slowly increase the temperature of the fluorinated polyamide compound or the fluorinated polyimide compound. The temperature increase rate may be 1 to 10°C / min. For example, the fluorinated polyamide compound or the fluorinated polyimide compound may be heated to 300 to 330°C, and then heated at a rate of 1 to 10°C / min so as to increase the temperature by 30°C or more.

[0114] The cured product of this embodiment has excellent low dielectric properties due to the skeleton of the fluorinated polyamide compound or fluorinated polyimide compound.

[0115] 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.

[0116] 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.

[0117] 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

[0118] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to these examples.

[0119] 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.

[0120] <Synthesis Example 1> Synthesis of 4,4'-(1,6-perfluorohexylene)diphthalic anhydride (6PFDAH)

[0121] [ka]

[0122] 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.

[0123] 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%

[0124] 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.

[0125] 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%

[0126] 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℃.

[0127] 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%

[0128] <Example 1> Synthesis of fluorinated polyimide compound (6PFDAH-TFMB)

[0129] [ka]

[0130] 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 onto a copper foil, and heated at 90 ° C for 30 minutes and at 250 ° C for 1 hour under 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 Example 1.

[0131] <Comparative Example 1> Synthesis of polyimide compound (6FDA-TFMB)

[0132] [ka]

[0133] A sample for evaluation in Comparative Example 1 was obtained in the same manner as in Example 1, except that 6FDA (0.841 g, 1.42 mmol) was used instead of 6PFDAH.

[0134] The physical properties of the resin compositions obtained in Example 1 and Comparative Example 1 are shown in Table 1 below.

[0135] [Table 1]

[0136] <Example 2> Resin composition made from fluorinated polyamide compound (6PFDAH-TFMB) (Filler weight ratio: 20.8%)

[0137] A mixture was prepared by mixing 2.37 g of a solution with a solid content concentration of 24 wt% obtained by dissolving the fluorinated polyamide compound (6PFDAH-TFMB) obtained in the middle of the process of Example 1 in cyclohexanone and 0.21 g of a cyclohexanone slurry with a solid content concentration of 70 wt% in which a spherical silica filler {SC2050-HNF (manufactured by Admatechs Co., Ltd.)} was dispersed. The overall concentration of the mixture was diluted by adding distilled NMP (2 ml) and stirring, and the mixture was applied onto a copper foil using an applicator with a gap of 200 μm. This was dried at 90 ° C for 5 minutes, and then heated at 250 ° C for 1 hour under a nitrogen atmosphere to obtain a film of a resin composition containing a fluorinated polyimide compound. The obtained resin composition film was peeled off from the copper foil to obtain an evaluation sample of Example 1.

[0138] <Comparative Example 2> Resin composition made from fluorinated polyamide compound (6PDA-TFMB) (Filler weight ratio: 20.8%)

[0139] A sample for evaluation of Comparative Example 2 was obtained in the same manner as in Example 2, except that the fluorinated polyamide compound (6PDA-TFMB) obtained during the process of Comparative Example 1 was used instead of the fluorinated polyamide compound (6PFDAH-TFMB) and the amounts of each component were set to the values ​​shown in Table 2.

[0140] The physical properties of the resin compositions obtained in Example 2 and Comparative Example 2 are shown in Table 2 below.

[0141] [Table 2]

[0142] <Example 3> Fluorinated polyamide compounds and fluorinated polyimide compounds (6PFDAH-TFMB-St)

[0143] [ka]

[0144] 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 Example 3, which is a precursor.

[0145] 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

[0146] <Example 4> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 20.4%, crosslinker weight ratio: 0%)

[0147] A curable composition was obtained by mixing and stirring 1.61 g of a fluorinated polyamide solution having a solid content of 24 wt%, which was prepared by dissolving the fluorinated polyamide compound powder of Example 3 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 PerbutylP40 (manufactured by NOF Corp.) (0.04 g). The curable composition was applied onto a copper foil using an applicator with a gap of 50 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 4 that was dehydrated, cyclized, and crosslinked. The cured product was peeled off from the glass substrate to prepare an evaluation sample of Example 4.

[0148] <Example 5> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 38.5%, crosslinker weight ratio: 0%)

[0149] An evaluation sample of Example 5 was prepared in the same manner as in Example 4, except that the blending amounts of each component were set to the values ​​shown in Table 3.

[0150] <Example 6> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 56.9%, crosslinker weight ratio: 0%)

[0151] An evaluation sample of Example 6 was prepared in the same manner as in Example 4, except that the blending amounts of each component were set to the values ​​shown in Table 3.

[0152] <Example 7> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 78.8%, crosslinker weight ratio: 0%)

[0153] An evaluation sample of Example 7 was prepared in the same manner as in Example 4, except that the blending amounts of each component were set to the values ​​shown in Table 3.

[0154] <Example 8> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 0.0%, crosslinker weight ratio: 0.0%) An evaluation sample of Example 8 was prepared in the same manner as in Example 4, except that no filler was added and the blending amounts of each component were set to the values ​​shown in Table 3.

[0155] The physical properties of each of the cured films of Examples 4 to 8 are shown in Table 3 below. The blend amounts in Table 3 indicate the solid content amounts.

[0156] [Table 3]

[0157] <Example 9> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 67.0%, crosslinker weight ratio: 6.0%)

[0158] An evaluation sample of Example 9 was prepared in the same manner as in Example 4, 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.

[0159] <Example 10> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 66.4%, crosslinker weight ratio: 11.2%)

[0160] An evaluation sample of Example 10 was prepared in the same manner as in Example 9, except that the blending amounts of each component were set to the values ​​shown in Table 4.

[0161] <Example 11> Cured material from fluorinated polyamide compound (6PFDAH-TFMB-St) (Filler weight ratio: 67.2%, crosslinker weight ratio: 16.0%)

[0162] An evaluation sample of Example 11 was prepared in the same manner as in Example 9, except that the blending amounts of each component were set to the values ​​shown in Table 4.

[0163] <Example 12> Cured material from fluorinated polyimide compound (6PFDAH-TFMB-St) (Filler weight ratio: 68.1%, crosslinker weight ratio: 0.0%)

[0164] An evaluation sample of Example 12 was prepared in the same manner as in Example 9, except that no crosslinking agent was added and the amounts of each component were set to the values ​​shown in Table 4.

[0165] The physical properties of each of the cured films of Examples 9 to 12 are shown in Table 4 below.

[0166] [Table 4] [Industrial Applicability]

[0167] The resin composition of the present invention and the cured product formed from the resin composition have excellent low dielectric tangent characteristics, and therefore can be suitably used as a low dielectric material for electronic parts, semiconductors, and electronic devices.

Claims

1. A resin composition comprising at least one of a fluorinated polyamide compound having a repeating structure represented by the following chemical formula (1) and a fluorinated polyimide compound having a repeating structure represented by 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, and L represents a linking group. 【Chemistry 2】 (In formula (2), m, n, ring A, ring B, R and L are as defined above.)

2. The resin composition according to claim 1 , further comprising a radical polymerization initiator, an acid generator, or a base generator.

3. The resin composition of claim 1 further comprising a crosslinking agent.

4. The resin composition according to claim 1 , further comprising a filler.

5. The resin composition according to claim 4 , wherein the content of the filler is 10% by mass or more based on the total solid content of the resin composition.

6. A cured product formed from the resin composition according to any one of claims 1 to 5.

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