CN118159521A

CN118159521A - Amide compound and curable resin composition containing same

Info

Publication number: CN118159521A
Application number: CN202280071313.9A
Authority: CN
Inventors: 田窪由纪; 中井诚; 小野辽平
Original assignee: Unitika Ltd
Current assignee: Unitika Ltd
Priority date: 2021-10-25
Filing date: 2022-10-19
Publication date: 2024-06-07
Also published as: JP7253300B1; JPWO2023074481A1

Abstract

The present invention provides a compound (particularly a curing agent) capable of obtaining a cured product which maintains heat resistance and mechanical properties and is excellent in flexibility and dielectric properties. The present invention relates to an amide compound represented by general formula (1) (in formula (1), R represents a hydrogen atom or an aryl group, X represents a divalent hydrocarbon group derived from an aliphatic dicarboxylic acid having 10 or more carbon atoms, Y represents a divalent hydrocarbon group derived from an aliphatic diamine having 10 or more carbon atoms, and n represents a number of 1 or more).

Description

Amide compound and curable resin composition containing same

Technical Field

The present invention relates to an amide compound and a curable resin composition containing the same.

Background

Curable resins such as epoxy resins are excellent in heat resistance, mechanical properties and electrical properties, and are widely used in industry mainly for electric and electronic materials such as insulating materials for printed wiring boards and semiconductor sealing materials.

In recent years, in the field of power semiconductors typified by in-vehicle power modules, further large-current, small-size, and high-efficiency are demanded, and a shift to silicon carbide (SiC) semiconductors is underway. Since SiC semiconductors can operate under conditions of higher temperature than conventional silicon (Si) semiconductors, semiconductor sealing materials used in SiC semiconductors are required to have higher heat resistance than conventional ones.

On the other hand, in the field of insulating materials for printed wiring boards, in order to increase the speed and frequency of signals in electronic devices and reduce the transmission loss of signals, excellent dielectric characteristics such as low dielectric constant and low dielectric loss tangent are required for insulating materials. Further, since the production and use in a high temperature region are increasing, flexibility is required for the insulating material in order to reduce cracking, peeling, and the like.

As a resin used for an electric/electronic material such as an insulating material for a printed wiring board or a semiconductor sealing material, for example, patent document 1 discloses a cured product of an epoxy resin using a compound having an imide structure. However, the cured product of patent document 1 is excellent in heat resistance, mechanical properties, and dielectric properties, but is insufficient in flexibility. It is generally known that heat resistance and flexibility are opposite properties, and it is difficult to achieve these properties.

Prior art literature

Patent literature

Patent document 1: international publication 2019/225166 booklet

Disclosure of Invention

The purpose of the present invention is to provide a compound (particularly a curing agent) that can provide a cured product that maintains heat resistance and mechanical properties and is excellent in flexibility and dielectric properties, and a curable resin composition using the compound.

As a result of intensive studies on the above problems, the present inventors have found that the above object is achieved by using an amide compound represented by the general formula (1) as a curing agent, and have completed the present invention.

Namely, the gist of the present invention is as follows.

< 1 > An amide compound represented by the general formula (1).

(In the formula (1), R represents a hydrogen atom or an aryl group, X represents a divalent hydrocarbon group derived from an aliphatic dicarboxylic acid having 10 or more carbon atoms, Y represents a divalent hydrocarbon group derived from an aliphatic diamine having 10 or more carbon atoms, and n represents a number of 1 or more.)

The amide compound according to < 2 > to < 1 >, wherein the number average molecular weight of the amide compound is 1000 or more.

< 3 > A curing agent consisting of an amide compound as described in < 1 > or < 2 >.

< 4 > A curable resin composition comprising the amide compound of < 1 > or < 2 > as a curing agent, and a curable resin.

The curable resin composition according to < 5 > to < 4 > further comprising a curing agent other than the amide compound.

The curable resin composition according to < 4 > or < 5 > wherein the curable resin is an epoxy resin.

The curable resin composition according to any one of < 4 > < 6 >, wherein the composition further comprises a curing accelerator.

The curable resin composition according to any one of < 4 > - < 7 >, wherein the ratio of the amide compound to the total of the curable resin and the curing agent is 35% by mass or less.

The curable resin composition according to any one of < 4 > - < 8 >, wherein the ratio of the amide compound to the total of the curable resin and the curing agent is 10 to 18 mass%.

The curable resin composition according to < 10> to < 9 >, wherein,

The curable resin composition further comprises a diimide dicarboxylic acid compound as a curing agent other than the amide compound,

The curable resin comprises bisphenol a type epoxy resin,

In the general formula (1), R represents a hydrogen atom, and n represents a number of 2 to 3.

A cured product of the curable resin composition of any one of < 11 > to <4 > to < 10 >.

< 12 > An electrically insulating material comprising the cured product of < 11 >.

< 13 > A sealing material comprising the cured product of < 11 >.

< 14 > The sealing material according to < 13 > for a power semiconductor module.

< 15 > A printed wiring board comprising the cured product described as < 11 >.

According to the present invention, a compound capable of obtaining a cured product excellent in flexibility and dielectric characteristics while maintaining good heat resistance and mechanical characteristics, and a curable resin composition using the compound can be provided.

The cured product obtained by curing the curable resin composition of the present invention can be applied to an electrical insulating material, a sealing material, and a printed wiring board.

Drawings

Fig. 1 is a TEM photograph showing the island-in-sea phase separation structure of the cured product of example 1.

Detailed Description

< Compounds >

The compound of the present invention is an amide compound represented by the general formula (1).

In the general formula (1), X represents a divalent hydrocarbon group derived from an aliphatic dicarboxylic acid having 10 or more carbon atoms. Specifically, X is a group (so-called residue) representing a structure of a portion other than an amide bond when the aliphatic dicarboxylic acid forms an amide bond, and may be a divalent saturated or unsaturated aliphatic hydrocarbon group. The above carbon number is the carbon number of the aliphatic dicarboxylic acid providing the X group. Accordingly, the number of carbon atoms of X (i.e., a divalent hydrocarbon group) corresponds to a value obtained by subtracting 2 from the number of carbon atoms of the aliphatic dicarboxylic acid. The aliphatic dicarboxylic acid having an X group is usually 10 to 50 carbon atoms, and is preferably 20 to 50, more preferably 30 to 42, and even more preferably 34 to 38 from the viewpoint of further improvement in heat resistance, mechanical properties, flexibility and dielectric properties.

Examples of aliphatic dicarboxylic acids providing the X group include sebacic acid (10 carbon atoms), dodecanedioic acid (12 carbon atoms), octadecanedioic acid (18 carbon atoms), nonadecanedioic acid (19 carbon atoms), icosanedioic acid (20 carbon atoms), heneicosanedioic acid (21 carbon atoms), docusanedioic acid (22 carbon atoms), tricosanedioic acid (23 carbon atoms), tetracosanedioic acid (24 carbon atoms), pentacosanedioic acid (25 carbon atoms), hexacosanedioic acid (26 carbon atoms), heptacosanedioic acid (27 carbon atoms), octacosanedioic acid (28 carbon atoms), nonadecanedioic acid (29 carbon atoms), triacontanoic acid (30 carbon atoms), triacontanedioic acid (31 carbon atoms), triacontanedioic acid (32 carbon atoms), tricontanedioic acid (33 carbon atoms), tetracosanediotricontanoic acid (34 carbon atoms), pentacosanedioic acid (35 carbon atoms), and dimer acid (36 carbon atoms). Among them, dimer acid is preferable from the viewpoint of high versatility and improved flexibility of the obtained cured product. Dimer acid is a compound obtained by, for example, subjecting 2 molecules of unsaturated fatty acid selected from oleic acid, linoleic acid and the like to addition reaction. The 2 molecules may be the same kind of molecules or may be different kinds of molecules from each other. The dimer acid may be a dicarboxylic acid having an unsaturated bond, or may be a dicarboxylic acid having a reduced degree of unsaturation by a hydrogenation reaction, depending on the purpose of use. The aliphatic dicarboxylic acid may be hydrogenated or may have a cyclic structure. The cyclic structure of the aliphatic dicarboxylic acid herein means a saturated carbocyclic ring having no aromaticity. The aliphatic dicarboxylic acid may have a branch or may have an unsaturated bond. The aliphatic dicarboxylic acid is preferably of high purity. Examples of commercial products of dimer acid include "Tsunodyme" from Toku Yedo Co., ltd., "PRIPOL1009" from Croda Japan, and "PRIPOL1004" from Croda Japan. One of the above-mentioned aliphatic dicarboxylic acids may be used alone, or two or more thereof may be used in combination.

In the general formula (1), Y represents a divalent hydrocarbon group derived from an aliphatic diamine having 10 or more carbon atoms. Specifically, Y is a group (so-called residue) representing a structure of a portion other than an amide bond when the aliphatic diamine forms an amide bond, and may be a divalent saturated or unsaturated aliphatic hydrocarbon group. The above carbon number is the carbon number of the aliphatic diamine providing the Y group. Therefore, the number of carbon atoms of Y (i.e., a divalent hydrocarbon group) corresponds to the same value as the number of carbon atoms of the aliphatic diamine. The aliphatic diamine having a Y group is usually 10 to 50 carbon atoms, and is preferably 20 to 50, more preferably 30 to 42, and even more preferably 34 to 38 from the viewpoint of further improvement in heat resistance, mechanical properties, flexibility and dielectric properties.

Examples of aliphatic diamines providing the Y group include decanediamine (10 carbon atoms), dodecanediamine (12 carbon atoms), octadecanediamine (18 carbon atoms), nonadecanediamine (19 carbon atoms), icosanediamine (20 carbon atoms), heneicosanediamine (21 carbon atoms), docosyl diamine (22 carbon atoms), tricosyl diamine (23 carbon atoms), tetracosanediamine (24 carbon atoms), pentacosamine (25 carbon atoms), hexacosediamine (26 carbon atoms), heptacosediamine (27 carbon atoms), octacosediamine (28 carbon atoms), nonacosediamine (29 carbon atoms), triacontane diamine (30 carbon atoms), triacontane diamine (31 carbon atoms), triacontane diamine (32 carbon atoms), triacontane diamine (33 carbon atoms), tetratriacontane diamine (34 carbon atoms), pentacontane diamine (35 carbon atoms), and dimer diamine (36 carbon atoms). Among them, dimer diamine is preferable from the viewpoint of high versatility and improved flexibility of the obtained cured product. Dimer diamine is a compound obtained by, for example, subjecting the above dimer acid to reduction and amination (reductive amination). The dimer diamine may be a diamine having an unsaturated bond, or may be a diamine having a reduced degree of unsaturation by hydrogenation, depending on the purpose of use. The aliphatic diamine may be hydrogenated or have a cyclic structure. The cyclic structure of the aliphatic diamine herein means a saturated carbocyclic ring having no aromaticity. The aliphatic diamine may have a branch or an unsaturated bond. The aliphatic diamine is preferably of high purity. Examples of commercial products of dimer diamine include "Versamine551" manufactured by BASF Japan, "Versamine552" manufactured by BASF Japan (hydride of Versamine 551), "PRIAMINE1075" manufactured by Croda Japan, and "PRIAMINE1074" manufactured by Croda Japan. The aliphatic diamine may be used alone or in combination of two or more.

In the general formula (1), each R independently represents a hydrogen atom or an aryl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. From the viewpoint of further improving heat resistance, mechanical properties, dielectric properties and flexibility, R is preferably a hydrogen atom.

In the general formula (1), n is an integer of 1 or more, preferably an integer of 2 or more, more preferably an integer of 3 or more, from the viewpoint of further improvement of mechanical properties and flexibility. If n is 0, heat resistance, mechanical properties and flexibility are lowered. The upper limit of n is not particularly limited, but n is usually an integer of 10 or less, particularly 5 or less, and is preferably an integer of 3 or less, more preferably 2, from the viewpoint of further improvement in heat resistance, mechanical properties, dielectric properties and flexibility.

The molecular weight of the amide compound of the present invention is preferably 1000 or more, more preferably 2000 to 5000, still more preferably 2000 to 4000, particularly preferably 2000 to 3000, from the viewpoint of further improvement of heat resistance, mechanical properties, dielectric properties and flexibility.

The molecular weight of the amide compound is a number average molecular weight, and a polystyrene equivalent measured by Gel Permeation Chromatography (GPC) is used.

The amide compound of the present invention can be used as a curing agent by using the compound in combination with a curable resin.

The method for producing the amide compound of the present invention is not particularly limited, and examples thereof include a method in which the aliphatic dicarboxylic acid is reacted with the aliphatic diamine to produce an amide compound, and then the trimellitic anhydride is reacted to perform a thermal ring-closure reaction. Further, if necessary, an esterification reaction may be performed to esterify the terminal. In the case of performing the esterification, a known esterification reaction may be performed, and examples thereof include a method of reacting a phenol with a catalyst and a method of using an ester exchange reaction.

Curable resin composition

The curable resin composition of the present invention can be obtained by mixing an amide compound represented by the general formula (1) with a curable resin.

Examples of the curable resin include epoxy resin, cyanate resin, phenolic resin, imide resin, maleimide resin, and benzo resinOxazine resin, silicone resin, acrylic resin, and fluororesin. Among them, epoxy resins are more preferable. The curable resin may be used alone or in combination of two or more.

The epoxy resin preferably has 2 or more epoxy groups in 1 molecule. Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, isocyanurate type epoxy resin, alicyclic epoxy resin, acrylic modified epoxy resin, polyfunctional epoxy resin, brominated epoxy resin, and phosphorus modified epoxy resin. The epoxy resin is preferably a difunctional epoxy resin such as a bisphenol a type epoxy resin or a biphenyl type epoxy resin, and more preferably a bisphenol a type epoxy resin, from the viewpoint of further improvement in heat resistance, mechanical properties, dielectric properties and flexibility. The epoxy equivalent of the epoxy resin is preferably 100 to 3000g/eq, more preferably 150 to 300g/eq.

The molecular weight of the curable resin is not particularly limited, and may be a molecular weight capable of achieving the above epoxy equivalent in the case of an epoxy resin, for example.

In order to further improve heat resistance, the curable resin composition of the present invention may contain other curing agents. The other curing agent is a curing agent having a structure different from that of the amide compound represented by the general formula (1). Examples of the other curing agent include phenolic curing agents (for example, novolak type phenolic resin curing agents), thiol type curing agents, amine type curing agents, acid anhydride type curing agents, cyanate type curing agents, active ester type curing agents, and imide type curing agents. Among them, from the viewpoint of further improvement of heat resistance, mechanical properties, dielectric properties and flexibility, an imide-based curing agent and/or a phenolic curing agent (particularly, a novolac-type phenolic resin curing agent) is preferable, and an imide-based curing agent is more preferable. The other curing agent may be used alone or in combination of two or more. By using other curing agents in combination with the amide compound of the present invention, a sea-island phase separation structure having the amide compound of the present invention as an island can be formed in the cured product. The heat resistance and mechanical properties can be more sufficiently maintained by using the other curing agent and the epoxy resin as sea components, and the amide compound and the epoxy resin of the present invention as island components can give a cured product which exhibits more sufficiently high flexibility and sufficiently excellent dielectric properties.

Examples of the imide-based curing agent include compounds having 1 to 4 imide groups and 2 to 4 glycidyl-reactive functional groups in the molecule. The glycidyl-reactive functional group means a functional group reactive with a glycidyl group, and may be, for example, a carboxyl group, a hydroxyl group, or an amine group. Examples of the imide-based curing agent include a compound obtained by reacting 2 trimellitic anhydride with 14, 4' -diaminophenyl ether (for example, a diimide dicarboxylic acid compound), a compound obtained by reacting 13, 3', 4' -benzophenone tetracarboxylic dianhydride with 2-amino terephthalic acid (for example, a diimide tetracarboxylic acid compound), and a compound obtained by reacting 1 trimellitic anhydride with 1 2-amino terephthalic acid (for example, a monoimide tricarboxylic acid compound). The imide curing agent is preferably a diimidedicarboxylic acid compound from the viewpoint of further improvement in heat resistance, mechanical properties, dielectric properties and flexibility.

In the curable resin composition of the present invention, the proportion of the amidation compound represented by the general formula (1) relative to the total of the curable resin and the curing agent is preferably 35% by mass or less (particularly 2 to 35% by mass), more preferably 20% by mass or less (particularly 10 to 20% by mass), still more preferably 18% by mass or less (particularly 10 to 18% by mass), still more preferably 10 to 15% by mass, and particularly preferably 12 to 14.5% by mass, from the viewpoint of further improving heat resistance, mechanical properties, dielectric properties and flexibility. The total of the curable resin and the curing agent means the total of the curable resin and the amide compound in the case where only the amide compound of the general formula (1) is used as the curing agent, and the total of the curable resin, the amide compound and the other curing agent in the case where the amide compound of the general formula (1) and the other curing agent are used as the curing agent.

In the curable resin composition of the present invention, the proportion of the curing agent (including the amide compound represented by the general formula (1)) is not particularly limited, but may be 80 to 120 mol% relative to the curable resin (100 mol%), and is preferably 90 to 110 mol% and more preferably 98 to 102 mol% from the viewpoint of further improvement in heat resistance, mechanical properties, dielectric properties and flexibility. When the curing agent contains the amide compound represented by the general formula (1) and other curing agents, the ratio of the curing agents is the total ratio of these.

The curable resin composition of the present invention may contain other additives such as a curing accelerator, an inorganic filler, an antioxidant, a flame retardant, and an organic solvent, within a range that does not impair the effects of the present invention.

Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; tertiary amines such as 4-dimethylaminopyridine, benzyl dimethylamine, 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (dimethylaminomethyl) phenol and the like; triphenylphosphine, tributylphosphine, and other organic phosphines. The curing accelerator may be used alone or in combination of two or more. When a curing accelerator is used, the amount of the curing accelerator is preferably 0.01 to 2.0% by mass, more preferably 0.01 to 1% by mass, and even more preferably 0.05 to 0.5% by mass, based on the total amount of the curable resin and the curing agent, from the viewpoint of improving the heat resistance and dielectric characteristics of the resulting cured product.

Examples of the inorganic filler include silica, barium sulfate, alumina, aluminum nitride, boron nitride, silicon nitride, glass frit, glass fiber, carbon fiber, and inorganic ion exchanger. The inorganic filler may be used alone or in combination of two or more. When the inorganic filler is used, the average particle diameter of the inorganic filler is preferably 50nm to 4. Mu.m, and more preferably 100nm to 3. Mu.m, from the viewpoint of further excellent coatability and workability.

Examples of the antioxidant include hindered phenol antioxidants, phosphorus antioxidants, and thioether antioxidants. The antioxidant may be used alone or in combination of two or more.

Examples of the flame retardant include non-halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, and silicone flame retardants. Among them, a non-halogen flame retardant is preferable from the viewpoint of environmental impact. The flame retardant may be used alone or in combination of two or more.

The organic solvent is not particularly limited as long as it can uniformly dissolve the curing agent and the curable resin and can be applied, and from the viewpoint of influence on the environment, a non-halogenated solvent is preferable. Examples of the non-halogenated solvent include N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone. The organic solvent may be used alone or in combination of two or more.

The method for producing the curable resin composition of the present invention is not particularly limited, and examples thereof include a method in which an amide compound represented by the general formula (1), a curable resin, and other additives, if necessary, are mixed using a mixer such as a homogenizer, a universal mixer, a Banbury mixer, or a kneader. From the viewpoint of dissolution of the components in an organic solvent, the components may be heated to 80 to 200 ℃ (particularly 100 to 150 ℃) during mixing.

< Cured object >)

By heating the curable resin composition of the present invention, the amide compound represented by the general formula (1) can be reacted with the curable resin to obtain a cured product. The heating temperature (curing temperature) is preferably 80 to 350 ℃, more preferably 130 to 300 ℃. The heating time (curing time) is preferably 1 minute to 24 hours, more preferably 5 minutes to 10 hours. In the case of a curable resin composition containing an organic solvent, the organic solvent is distilled off by heating.

In the present invention, the characteristic value of the cured product was evaluated by comparing with a specific cured product having no soft component. The "specific cured product having no softening component" refers to a cured product containing a specific other curing agent in place of the amide compound represented by the general formula (1). The specific other curing agent means the other curing agent when the curable resin composition of the present invention constituting the cured product to be evaluated contains a curable resin, an amide compound represented by the general formula (1), and the other curing agent. When the curable resin composition contains two or more other curing agents, the largest amount of the other curing agents contained is referred to as "specific other curing agents". Therefore, in the case where the curable resin composition of the present invention contains a curable resin, an amide compound represented by the general formula (1), and other curing agents, the characteristic value of the cured product of the present invention produced from the curable resin composition is evaluated by comparing with a cured product produced by the same method as the cured product of the present invention except that other curing agents are used in place of the amide compound (i.e., "specific cured product having no soft component").

From the viewpoint of heat resistance, the difference between the glass transition temperature of the cured product of the present invention and the glass transition point of the "specific cured product having no soft component" is preferably 20 ℃ or less, more preferably 10 ℃ or less.

From the viewpoint of flexibility, the tensile elastic modulus of the cured product of the present invention is preferably 75% or less, more preferably 70% or less, and even more preferably 65% or less, as compared with "a specific cured product having no soft component".

The tensile breaking strength of the cured product of the present invention is preferably 60% or more, more preferably 65% or more, and still more preferably 70% or more, from the viewpoint of mechanical properties, as compared with "a specific cured product having no soft component".

The dielectric loss tangent of the cured product of the present invention is preferably not more than the dielectric loss tangent of the "specific cured product having no soft component", and more preferably less than the dielectric loss tangent of the "specific cured product having no soft component".

< Use of cured article >

The cured product of the present invention is excellent in flexibility and dielectric characteristics while maintaining heat resistance and mechanical characteristics, and therefore can be suitably used for an electrical insulating material. Specifically, the cured product of the present invention can be applied to a sealing material (for example, a sealing material for a power semiconductor module), a printed wiring board, a molding material (for example, a molding material for a bushing transformer, a molding material for a solid insulation switchgear), an electrical penetration member for a nuclear power plant, a stacked laminate, an interlayer insulating material (for example, an organic redistribution layer, an insulating adhesive film), a photosensitive insulating material, a conductive paste, and the like. Among them, the cured product of the present invention is more preferably used for a sealing material, a printed wiring board, and an interlayer insulating material.

For example, in the case where the cured product of the present invention is used as a sealing material (in particular, an insulating material for a sealing material), the cured product of the present invention can be obtained by producing a power semiconductor module, filling an epoxy resin solution (in particular, the curable resin composition of the present invention) into a mold provided with the module, and drying and curing the resin solution.

In addition, for example, in the case where the cured product of the present invention is used as a printed wiring board (particularly, an insulating material for a printed wiring board), the cured product of the present invention can be obtained by impregnating or coating an epoxy resin solution (particularly, the curable resin composition of the present invention) on a glass cloth, followed by drying and curing.

Further, for example, in the case where the cured product of the present invention is used as an interlayer insulating material, the cured product of the present invention can be obtained by processing an epoxy resin solution (particularly, the curable resin composition of the present invention) into a sheet form, drying the sheet, and laminating the sheet on both surfaces of an inner substrate in this state, and curing the sheet.

Examples

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

A. Raw materials

The raw materials used in examples and comparative examples are shown below.

(A) Curable resin

Bisphenol a epoxy resin: manufactured by Tokyo chemical industry Co., ltd., epoxy equivalent weight of 170g/eq

Biphenyl type epoxy resin: "YX4000H", of Mitsubishi chemical Co., ltd., epoxy equivalent weight 180g/eq

(B) Raw materials of curing agent and curing agent

Dimer acid: PRIPOL1009, manufactured by Croda Japan Inc "

Dimer diamine: "PRIAMINE1075" manufactured by Croda Japan Co "

Trimellitic anhydride: manufactured by Tokyo chemical industry Co Ltd

4,4' -Diaminodiphenyl ether: manufactured by Tokyo chemical industry Co Ltd

Acetic acid 1-naphthalenyl ester: manufactured by Tokyo chemical industry Co Ltd

Novolac type phenolic resin: "PHENOLITE TD-2131" manufactured by DIC Co "

Poly (propylene glycol) bis (2-aminopropyl ether): HUNTSMAN Co., ltd. "ELASTAMINE RP-2009", molecular weight 2000

Imide dicarboxylic acid F

50 Parts by mass of dimer diamine and 35.9 parts by mass of trimellitic anhydride were mixed and pulverized at a rotational speed of 9000rpm for 3 minutes using Wonder Crusher WC-3C manufactured by Osaka chemical Co. The treated sample was transferred into a glass container, and imidization was performed at 300℃for 2 hours under a nitrogen atmosphere using an inert furnace DN411I manufactured by Yamato Scientific, to obtain a diimide dicarboxylic acid F.

As a result of ¹ H-NMR analysis, the structure represented by the general formula (1) (n=0, R is a hydrogen atom, and Y is a dimer diamine residue) was obtained. The number average molecular weight of the diimide dicarboxylic acid E was 890, and the product was solid at room temperature.

Imide dicarboxylic acid G

61.4 Parts by mass of diimine dicarboxylic acid F and 38.6 parts by mass of 1-naphthalene acetate were charged into a reaction vessel equipped with a heating mechanism and a stirring mechanism. Then, the reaction was carried out under nitrogen flow at normal pressure for 3 hours while heating at 300℃under stirring and removing the condensed water from the system. Then, the reaction mixture was washed with methanol and dried to obtain an imide dicarboxylic acid G.

As a result of the examination of the diimine dicarboxylic acid G by ¹ H-NMR and GPC, the structure represented by the general formula (1) (n=0, R is a naphthyl group, and Y is a dimer diamine residue). The number average molecular weight of the imide dicarboxylic acid G was 1137, and was solid at room temperature.

Imide dicarboxylic acid H

The same procedure as for the preparation of the imide dicarboxylic acid F was repeated except that 50 parts by mass of dimer diamine was replaced with 18.8 parts by mass of 4,4' -diaminodiphenyl ether, to obtain an imide dicarboxylic acid H.

As a result of the ¹ H-NMR examination, the diimide dicarboxylic acid H was a compound composed of trimellitic acid-4, 4' -diaminodiphenyl ether-trimellitic acid. The number average molecular weight of the diimide dicarboxylic acid H was 549, and was a solid at ordinary temperature.

(C) Curing accelerator

2-Ethyl-4-methylimidazole: manufactured by Tokyo chemical industry Co Ltd

(D) Organic solvents

N, N-dimethylformamide: manufactured by Tokyo chemical industry Co Ltd

Toluene: manufactured by Tokyo chemical industry Co Ltd

B. Evaluation method

The compounds and cured products obtained in examples and comparative examples were evaluated as follows.

In particular, the comparison object (or comparison standard) in evaluating the cured products obtained in examples and comparative examples is "specific cured product having no soft component", as follows.

The cured products of examples 1 to 7 and comparative examples 1 to 4 were compared with the cured product of reference example 1.

The cured product of example 8 was compared with the cured product of reference example 2.

The cured product of example 9 was compared with the cured product of reference example 3.

(1) Composition of curing agent (Compounds A to G)

The curing agent was analyzed by ¹ H-NMR using a high-resolution nuclear magnetic resonance apparatus (JNM-ECA 500 NMR, manufactured by Japanese electronics Co., ltd.) and the resin composition (resolution: 500MHz, solvent: deuterated dimethyl sulfoxide, temperature: 25 ℃ C.) was determined from the peak intensities of the respective copolymer components.

(2) Number average molecular weight of curing agent (Compounds A to G)

The Gel Permeation Chromatograph (GPC) was used to measure GPC of standard polystyrene under the following conditions to prepare a standard curve, and then the curing agents (compounds a to G) were used to measure GPC under the same conditions to determine average molecular weight in terms of polystyrene.

< GPC measurement conditions >

The device comprises: HLC-8220GPC manufactured by Tosoh Co., ltd

Column: shodex GPC KF-405L HQ 3 root manufactured by Showa electric company

Solvent: chloroform (chloroform)

Flow rate: 0.3mL/min

Temperature: column 40 DEG C

Sample concentration: 0.2 mass%

A detector: RI detector

Calibration samples: standard polystyrene

(3) Glass transition temperature (heat resistance) of cured product

The cured products obtained in examples and comparative examples were measured using a Differential Scanning Calorimeter (DSC) under the following conditions.

< Measurement Condition >

The device comprises: PERKIN ELMER DSC 6000

Heating rate: 10 ℃/min

The temperature was raised from 25 ℃ to 300 ℃, and the starting temperature of discontinuous change of the transition temperature from the obtained temperature-raising curve was set as the glass transition temperature.

The value a was obtained according to the following equation, and evaluated according to the following criteria.

A value = [ "glass transition temperature of specific cured product having no softening component ] - [ glass transition temperature of cured product obtained in examples and comparative examples ]

< Evaluation criterion >

And (3) the following materials: below 20 deg.c (best)

X: exceeding 20 ℃ (bad)

(4) Tensile elastic modulus (flexibility) and tensile breaking strength (mechanical properties) of the cured product

The cured products obtained in examples and comparative examples were cut into test pieces having a width of 10X a length of 100mm, and the test pieces were measured in accordance with ISO 178.

The values B and C were obtained according to the following formulas, and evaluated according to the following criteria.

< Evaluation of tensile elastic modulus >

B value = [ tensile elastic modulus of cured products obtained in examples and comparative examples ]/[ "tensile elastic modulus of specific cured product having no softening component ] ×100 ]

And (3) the following materials: the B value is less than or equal to 65 percent (best)

O: the B value is more than 65 percent and less than or equal to 70 percent (good)

Delta: the B value is more than 70 percent and less than or equal to 75 percent (in general)

X: 75% < B value (bad)

< Evaluation of tensile breaking Strength >

C value = [ tensile breaking strength of cured products obtained in examples and comparative examples ]/[ "tensile breaking strength of specific cured product having no softening component ] ×100 ]

And (3) the following materials: c value of 70% or less (best)

O: c value is more than or equal to 65% and less than 70% (good)

Delta: c value is more than or equal to 60% and less than 65% (good)

X: c value < 60% (bad)

(5) Dielectric loss tangent (dielectric characteristics) of cured product

The dielectric loss tangent of the cured products obtained in examples and comparative examples was measured under the following conditions using the following apparatus.

< Measurement Condition >

The device comprises: PNA network analyzer N5222B manufactured by Keysight Technologies company

CP-521 for cavity resonator 5.8GHz manufactured by Kanto electronic application development Co

Sample size: length 80mm x width 2mm x thickness 100 μm

Frequency: 5.8GHz

Measuring temperature: 23 DEG C

Test environment: 23 ℃ + -1 ℃, 50%RH+ -5%RH

The dielectric loss tangent of the cured product having no soft component (reference example) was compared with that of the cured product having no soft component, and the cured product was evaluated according to the following criteria.

Evaluation of dielectric loss tangent

And (3) the following materials: the cured products obtained in examples and comparative examples had a lower dielectric loss tangent than the "specific cured product having no soft component";

O: the dielectric loss tangent of the cured product obtained in examples and comparative examples was the same as (generally) that of "specific cured product having no soft component"; and

X: the cured products obtained in examples and comparative examples had a dielectric loss tangent higher (poor) than that of "specific cured products having no soft component".

(6) Phase separation structure of cured product

The cured products obtained in examples and comparative examples were sliced with a thickness of 80nm using a RAIKA: EMUC-7 microtome, and the phase separation structure was observed under the following conditions. Fig. 1 shows a TEM photograph showing the island-in-sea phase separation structure of the cured product of example 1.

< Measurement Condition >

The device comprises: JEM-1230TEM manufactured by Nippon Electron Co., ltd

The measuring method comprises the following steps: transmission measurement

Measurement conditions: accelerating voltage of 100kV

The obtained TEM photographs were evaluated according to the following criteria.

< Evaluation of phase separation Structure >

And (3) the following materials: has the sea-island type phase separation structure shown in FIG. 1.

X: does not have the island-in-the-sea phase separation structure shown in fig. 1.

(7) Comprehensive evaluation

Based on the results of the evaluation of heat resistance, mechanical properties, dielectric properties and flexibility, comprehensive evaluation was performed.

And (3) the following materials: all the evaluation results were excellent.

O: the lowest evaluation result was o among all the evaluation results.

Delta: the lowest evaluation result among all the evaluation results was Δ.

X: of all the evaluation results, the lowest evaluation result was x.

Example 1

(Compound A)

35.2 Parts by mass of dimer acid and 50 parts by mass of dimer diamine were charged into a reaction vessel equipped with a heating mechanism and a stirring mechanism. Then, the polymerization was carried out under nitrogen flow at normal pressure for 2 hours while heating at 230℃under stirring and removing the condensed water from the system. Then, the mixture was cooled to 50℃and 11.9 parts by mass of trimellitic anhydride was charged. Heating at 210 ℃ again under stirring, and carrying out heating ring-closure reaction for 1 hour to obtain the compound A.

As a result of the examination of compound A by ¹ H-NMR and GPC, the structure represented by general formula (1) (n=2, R is a hydrogen atom, Y is a dimer diamine residue, and X is a dimer acid residue). The compound A had a number average molecular weight of 2762 and was a viscous liquid at ordinary temperature.

(Curable resin composition)

The compound a, bisphenol epoxy resin, imide dicarboxylic acid H, 2-ethyl-4-methylimidazole, and N, N-dimethylformamide were dissolved by circulating heating at 130 ℃ for 0.5 hour at the compounding ratios shown in table 1. After cooling, other additives were mixed and stirred to obtain a curable resin composition.

(Cured product)

The obtained curable resin composition was applied to an aluminum substrate at a thickness of 300. Mu.m, dried at 120℃for 1 hour in a nitrogen atmosphere using an inert furnace, then heated to 300℃over 8 hours, and dried at 300℃for 1 hour, and desolvation and curing reactions were carried out.

Then, the aluminum base material was removed from the aluminum base material on which the resin layer was formed, to obtain a cured product. The thickness of the cured product was 100. Mu.m.

Example 2

(Compound B)

Compound B was obtained in the same manner as in example 1, except that 35.2 parts by mass of dimer acid was replaced with 42.2 parts by mass and 11.9 parts by mass of trimellitic anhydride was replaced with 7.1 parts by mass.

As a result of confirming the compound B by ¹ H-NMR and GPC, the structure represented by the general formula (1) (n=4, R is a hydrogen atom, Y is a dimer diamine residue, and X is a dimer acid residue). The number average molecular weight of the compound B was 4900, and the compound B was a viscous liquid at ordinary temperature.

The same procedure as in example 1 was repeated except that the blending amount of the obtained compound B was changed so as to have the composition shown in table 1, to prepare a curable resin composition and a cured product.

Example 3

(Compound C)

Compound C was obtained in the same manner as in example 1, except that 35.2 parts by mass of dimer acid was replaced with 26.4 parts by mass and 11.9 parts by mass of trimellitic anhydride was replaced with 17.8 parts by mass.

As a result of confirming the compound C by ¹ H-NMR and GPC, the structure represented by the general formula (1) (n=1, R is a hydrogen atom, Y is a dimer diamine residue, and X is a dimer acid residue). The compound C had a number average molecular weight of 1861 and was semi-solid at ordinary temperature.

The same procedure as in example 1 was repeated except that the blending amount of the obtained compound C was changed so as to have the composition shown in table 1, to prepare a curable resin composition and a cured product.

Example 7

(Compound D)

84.7 Parts by mass of compound A and 15.3 parts by mass of 1-naphthalate acetate were charged into a reaction vessel equipped with a heating mechanism and a stirring mechanism. Then, the reaction was carried out under nitrogen flow at normal pressure for 3 hours while heating at 300℃under stirring and removing the condensed water from the system. Then, the mixture was washed with methanol and dried to obtain compound D.

As a result of confirming the compound D by ¹ H-NMR and GPC, the structure represented by the general formula (1) (n=2, R is a naphthyl group, Y is a dimer diamine residue, and X is a dimer acid residue). The number average molecular weight of the compound D was 3273, and the compound D was a viscous liquid at ordinary temperature.

The same procedure as in example 1 was repeated except that the amount of the compound D obtained was changed so as to have the composition shown in table 1, to prepare a curable resin composition and a cured product.

Comparative example 1

(Polyamide E)

50 Parts by mass of dimer acid and dimer diamine were charged into a reaction vessel equipped with a heating mechanism and a stirring mechanism. Then, the mixture was heated at 230℃with stirring, and the polymerization was carried out under a nitrogen flow at normal pressure for 2 hours while removing the condensed water from the system, to obtain polyamide E.

As a result of confirming that polyamide D was a structure obtained by alternately polymerizing dimer acid and dimer diamine by ¹ H-NMR and GPC. The polyamide E had a number average molecular weight of 2703 and was a viscous liquid at ordinary temperature.

The same procedure as in example 1 was repeated except that the blending amount of the polyamide E thus obtained was changed so as to have the composition shown in table 2, to prepare a curable resin composition and a cured product.

Examples 4 to 9, comparative examples 2 to 4 and reference examples 1 to 3

The same procedure as in example 1 was repeated except that the raw materials and the blending amounts were changed so as to have the compositions shown in tables 1 to 3, and a curable resin composition was produced and a cured product was produced.

The composition of the curable resin composition and the evaluation results of the obtained cured product are shown in the table.

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The cured products of examples 1 to 6 each used a compound of the general formula (1) wherein R was a hydrogen atom, X was a divalent hydrocarbon group derived from an aliphatic dicarboxylic acid having 10 or more carbon atoms, Y was a divalent hydrocarbon group derived from an aliphatic diamine having 10 or more carbon atoms, and n was a number of 1 or more, and as a result, had a sea-island type phase separation structure. Accordingly, the cured products of examples 1 to 6 were obtained by using a specific cured product having no soft component (reference example 1), a difference in glass transition temperature of 20℃or lower, a tensile breaking strength of 60% or higher, a dielectric loss tangent of less, and a tensile elastic modulus of 75% or lower. As a result, the cured products of examples 1 to 6 were excellent in flexibility and dielectric characteristics while maintaining heat resistance and mechanical characteristics.

The cured product of example 7 was obtained by using a compound having a formula (1) in which R is a naphthyl group, X is a divalent hydrocarbon group derived from an aliphatic dicarboxylic acid having 10 or more carbon atoms, Y is a divalent hydrocarbon group derived from an aliphatic diamine having 10 or more carbon atoms, and n is a number of 1 or more, and as a result, it had a sea-island type phase separation structure. Therefore, the cured product of example 7 was found to have a difference in glass transition temperature of 20 ℃ or lower, a tensile breaking strength of 60% or higher, a smaller dielectric loss tangent, and a tensile elastic modulus of 75% or lower, relative to the "specific cured product having no soft component" (reference example 1). As a result, the cured product of example 7 was excellent in flexibility and dielectric characteristics while maintaining heat resistance and mechanical characteristics.

The cured product of example 8 was obtained by using a compound having a formula (1) in which R is a hydrogen atom, X is a divalent hydrocarbon group derived from an aliphatic dicarboxylic acid having 10 or more carbon atoms, Y is a divalent hydrocarbon group derived from an aliphatic diamine having 10 or more carbon atoms, and n is a number of 1 or more, and as a result, it had a sea-island type phase separation structure. Therefore, the cured product of example 8 was found to have a difference in glass transition temperature of 20 ℃ or lower, a tensile breaking strength of 60% or higher, a smaller dielectric loss tangent, and a tensile elastic modulus of 75% or lower, relative to the "specific cured product having no soft component" (reference example 2). As a result, the cured product of example 8 was excellent in flexibility and dielectric characteristics while maintaining heat resistance and mechanical characteristics.

The cured product of example 9 was obtained by using a compound having the general formula (1) wherein R is a hydrogen atom, X is a divalent hydrocarbon group derived from an aliphatic dicarboxylic acid having 10 or more carbon atoms, Y is a divalent hydrocarbon group derived from an aliphatic diamine having 10 or more carbon atoms, and n is a number of 1 or more, and as a result, it had a sea-island type phase separation structure. Therefore, the cured product of example 9 was found to have a difference in glass transition temperature of 20 ℃ or lower, a tensile breaking strength of 60% or higher, a smaller dielectric loss tangent, and a tensile elastic modulus of 75% or lower, relative to the "specific cured product having no soft component" (reference example 3). As a result, the cured product of example 9 was excellent in flexibility and dielectric characteristics while maintaining heat resistance and mechanical characteristics.

Since the cured product of comparative example 1 uses a polyamide composed of dimer acid and dimer diamine, the tensile breaking strength is less than 60% relative to the "specific cured product having no soft component" (reference example 1).

Since the amide compound represented by the general formula (1) was not used for the cured product of comparative example 2, the difference in glass transition temperature was more than 20℃and the tensile elastic modulus was more than 75% relative to the "specific cured product having no soft component" (reference example 1).

Since the amide compound represented by the general formula (1) was not used for the cured product of comparative example 3, the dielectric loss tangent was larger than that of the "specific cured product having no soft component" (reference example 1).

The cured product of comparative example 4 did not use the amide compound represented by the general formula (1), and therefore had a difference in glass transition temperature of more than 20℃and a tensile elastic modulus of more than 75% relative to the "specific cured product having no soft component" (reference example 1).

Industrial applicability

The amide compound of the present invention is used as a cured product of a curing agent, and is excellent in heat resistance, mechanical properties, flexibility and dielectric properties, and therefore, can be suitably used for materials (for example, electric insulating materials) requiring at least one of these properties.

Claims

1. An amide compound represented by the general formula (1),

In the formula (1), R represents a hydrogen atom or an aryl group, X represents a divalent hydrocarbon group derived from an aliphatic dicarboxylic acid having 10 or more carbon atoms, Y represents a divalent hydrocarbon group derived from an aliphatic diamine having 10 or more carbon atoms, and n represents a number of 1 or more.

2. The amide compound according to claim 1, wherein the number average molecular weight of the amide compound is 1000 or more.

3. A curing agent composed of the amide compound according to claim 1 or 2.

4. A curable resin composition comprising the amide compound according to claim 1 or 2 as a curing agent, and a curable resin.

5. The curable resin composition according to claim 4, further comprising a curing agent different from the amide compound.

6. The curable resin composition according to claim 4, wherein the curable resin is an epoxy resin.

7. The curable resin composition according to claim 4, further comprising a curing accelerator.

8. The curable resin composition according to claim 4, wherein the ratio of the amide compound to the total of the curable resin and the curing agent is 35% by mass or less.

9. The curable resin composition according to claim 4, wherein the proportion of the amide compound to the total of the curable resin and the curing agent is 10 to 18 mass%.

10. The curable resin composition according to claim 9, wherein,

The curable resin comprises bisphenol a type epoxy resin,

11. A cured product obtained by curing the curable resin composition according to claim 4.

12. An electrical insulating material comprising the cured product of claim 11.

13. A sealing material comprising the cured product according to claim 11.

14. The sealing material according to claim 13, which is used for a power semiconductor module.

15. A printed wiring board comprising the cured product according to claim 11.