JP2000080344A - Resin composition and bonding method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve heat resistance, insulating properties and adhesiveness at a high temperature of a resin composition by blending an aromatic polyamide resin having a phenolic hydroxide group and a specific linear polyamide resin. SOLUTION: An aromatic polyamide resin having a phenolic hydroxide group which resin comprises 5-100 mol% of a repeating unit of formula I and 0-95 mol% of a repeating unit of formula II is obtained by reacting an aromatic diamine compound having at least one alkyl group on the ortho-position of the terminal amino aryl group and an aromatic dicarboxylic acid having a phenolic hydroxide group. 1-70 pts.wt. of the aromatic polyamide resin is blended with an alcohol-soluble linear polyamide resin whose amide groups are partially di-methylated in the amount such that the total be 100 pts.wt. In the formulas, Ar is a bivalent aromatic group, R and R' are each H or a 1-4C alkyl but both are not H simultaneously, R2 is a 1-3C alkylene which may be substituted by F, and (n) is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition used for bonding components such as electric or electronic equipment, and more particularly to bonding an insulated wire for a coil or a coil supporting member requiring heat resistance and insulation. For example, the present invention relates to a resin composition suitable for bonding equipment parts which need to maintain an adhesive force under a high temperature environment, and a bonding method using the resin composition.

[0002]

2. Description of the Related Art In recent years, miniaturization and high performance of electric and electronic devices have been remarkable, and components used therein have also been required to have high performance. In particular, resin materials are required to have high insulation properties and high heat resistance. In the field of electric wires, a self-fusing magnet wire obtained by applying and baking a fusion coating on a conductor via an insulating coating is easily melted, swelled or melted by solvent treatment or heat treatment. Since they can be fused and solidified, self-supporting coils such as flat coils, deflection yoke coils, and voice coils can be made relatively easily, and are widely used for coil windings of complicated shapes. . As a method of manufacturing this coil, a self-fusing magnet wire is treated with a solvent to dissolve, swell, and adheres by bonding, and a fusion coating of the self-fusing magnet wire is heated by hot air or the like. There is a heat bonding type that bonds after melting. At the time of coil winding, whether to perform a solvent treatment or a heat treatment on the self-fusing magnet wire is determined by the characteristics of the fusion coating. Polyvinyl butyral resin, phenoxy resin, polyamide resin and the like are conventionally known as a resin used as a main component resin of the fusion coating, but a solvent bonding type wire and a heat bonding type wire are taken into consideration in consideration of bonding characteristics, electric characteristics and the like. In both cases, polyamide resins are relatively frequently used. In the production of a solvent-bonded wire, there is no limitation on the type of solvent as long as it is a good solvent for the resin forming the fusion coating, but an alcohol wound type using an alcohol solvent is often used in consideration of its handleability. . Alcohol-soluble polyamide resins are frequently used as the resin used for the alcohol wound type fusion coating. As the alcohol-soluble polyamide resin, Ultramid 1C (manufactured by BASF), Platabond MX1603 (manufactured by Nippon Rilsan), Amilan CM40 (manufactured by Toray), which is a copolymer of 6-10 nylon and 6 or 6,6-nylon, etc. Is known.

[0003] On the other hand, the heat-bonding type wire is made of an alcohol-insoluble polyamide resin such as Grilamide ELY60 (manufactured by EMS Japan), Daiamide L1801 (manufactured by Daicel), Platabond M, as a resin used for the fusion coating.
1426 (manufactured by Nippon Rilsan Co., Ltd.) or the like can be used. However, these aliphatic polyamide resins are thermoplastic, and by using a resin having a high melting point, it is possible to improve the heat resistance to some extent. Distortion and displacement of the fused surface were inevitable. Therefore, in order to improve heat resistance and improve adhesiveness in a high-temperature environment, an attempt has been made to mix a thermosetting resin, such as an epoxy resin or a phenol resin, with these polyamide resins, and to heat and cure after winding. ing. However, these thermosetting resins have poor flexibility when formed into a film,
When added in a large amount, the coating amount is limited due to problems such as cracking of the coating during winding, and sufficient heat resistance cannot be obtained with a small amount added. In the thermosetting resin, heat curing occurs in the step of applying and drying the paint on the adherend, and in the case of the heat bonding type, the melt fluidity of the film is insufficient in the subsequent heat bonding step, and satisfactory adhesive strength is obtained. There were no cases. On the other hand, in the alcohol-wound type, as the curing progresses, the resolubility in alcohol deteriorates, and there has been a problem that sufficient adhesiveness cannot be obtained during subsequent solvent adhesion.

[0004] The heat bonding type wire is superior to the solvent bonding type wire in the alignment winding property, and can be used in a wide range because it can obtain a coil with high dimensional accuracy and has high versatility, and the process can be easily automated. I have. On the other hand, a solvent-bonded wire can be used with a resin having a high melting point as long as it is soluble in a solvent, and is therefore applied to the manufacture of coils in fields requiring heat resistance. However, as described above, in the production of conventional coils, there has been no coil coating paint and adhesive method that have sufficient heat resistance and good adhesive strength regardless of which bonding method is used. Therefore, there has been a demand for a coating material and a bonding method which can be applied to both processes and have high heat resistance, high insulation properties and high bonding strength.

In the field of laminate production, a heat-resistant insulating resin solution is applied to one side of a metal foil to obtain a dried and cured metal foil with a heat-resistant insulating layer. 2. Description of the Related Art A manufacturing method in which a prepreg is interposed and laminated integrally by applying heat and pressure is conventionally known. In order to improve the heat resistance of the laminate, a metal-clad plate using various heat-resistant resins is used. For example, there are a polyimide resin-based copper-clad board, a polysulfone resin-based copper-clad board, a fluororesin-based copper-clad board, and the like. However, these heat-resistant substrates require a special high-temperature press because of the need to apply heat at a high temperature when integrated lamination, and are economically scarce because of the expensive materials. There is a problem that must be done. Furthermore, because of poor adhesion to the metal plate, it is necessary to use specially treated copper foil,
A method of modifying a heat-resistant resin with an epoxy resin or the like has been used. As described above, various complicated methods have been used, but a heat-resistant laminate having satisfactory practical characteristics has not been obtained. Therefore, there has been a demand for a highly heat-resistant paint and a bonding method that can provide sufficient adhesiveness by a heat-pressure treatment at a temperature as low as possible and that can produce a heat-resistant laminate.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems of the prior art, and in particular, it has been proposed to manufacture windings such as coils and laminates requiring heat resistance, and to provide other means. It is an object of the present invention to provide a resin composition which can be easily bonded by either a solvent bonding type or a heat bonding type in bonding electric and electronic components to each other, and a bonding method using the same.

[0007]

The resin composition of the present invention comprises:
A resin composition containing at least an aromatic polyamide resin having a phenolic hydroxyl group (hereinafter, aramid resin) and a linear polyamide resin in which a part of an amide group is methoxymethylated. In the bonding method of the present invention using the resin composition, as a first method, the resin composition of the present invention is applied to the surface of the adherend A and dried to form a resin film on the surface of the adherend A. Heating the resin coating surface;
And a step of superposing and bonding the adherend B to the heated resin film surface. As a second method, a step of applying the resin composition of the present invention to the surface of the adherend A and drying it to form a resin film on the surface of the adherend A; and superposing the adherend B on the surface of the resin film And adhering the adherend A and the adherend B by heating the resin film.

[0008] As a third method, a step of applying the resin composition of the present invention to the surface of the adherend A and drying to form a resin film on the surface of the adherend A; dissolving the resin film on the surface of the resin film A step of applying a possible solvent; and a step of superposing and bonding the adherend B to the resin coating surface. As a fourth method, a step of applying the resin composition of the present invention to the surface of the adherend A and drying to form a resin film on the surface of the adherend A; a solvent capable of dissolving the resin film on the surface of the resin film; A step of applying; and a step of superposing the adherend B on the surface of the resin film and then heating and bonding the same.

Hereinafter, the present invention will be described in detail. The present invention comprises at least an aramid resin having a phenolic hydroxyl group having good heat resistance and a linear polyamide resin in which a part of an amide group having good self-fusion property is methoxymethylated. Provided is a resin composition having a low adhesive strength and having excellent self-fusing properties and excellent heat resistance. The ratio of the aramid resin in the resin composition of the present invention is preferably 1 to 70 parts by weight, more preferably 10 to 50 parts by weight, when the resin component obtained by adding the aramid resin and the linear polyamide resin is 100 parts by weight. It is.

The aromatic polyamide resin is synthesized by a condensation reaction between an aromatic dicarboxylic acid and an aromatic diamine.
Similarly, the aromatic polyamide resin having a phenolic hydroxyl group used in the present invention includes at least one component, that is, an aromatic dicarboxylic acid component and an aromatic diamine component including at least a phenolic hydroxyl group-containing aromatic dicarboxylic acid, and an aromatic dicarboxylic acid. Aromatic diamine component containing an acid component and at least a phenolic hydroxyl group-containing aromatic diamine component, or aromatic diamine containing at least a phenolic hydroxyl group-containing aromatic dicarboxylic acid and an aromatic dicarboxylic acid component and at least a phenolic hydroxyl group-containing aromatic diamine It is produced by the condensation reaction between carboxyl groups and amino groups of these components using the components. These components used in the present invention are not limited at all, and can be used for the purpose of the present invention.

The aromatic dicarboxylic acid for synthesizing the aromatic polyamide resin having a phenolic hydroxyl group used in the present invention is exemplified below. For example, isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 3,
3′-methylene dibenzoic acid, 4,4′-methylene dibenzoic acid, 4,4′-oxydibenzoic acid, 4,4′-thiodibenzoic acid, 3,3′-carbonyl dibenzoic acid, 4, 4 '
-Carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, phenylmalonic acid, benzylmalonic acid, phenylsk Sinic acid, phenylglutaric acid, homophthalic acid, 1,3
-Phenylene diacetate, 1,4-phenylene diacetate, 4-
Carboxyphenylacetic acid, 5-bromo-N- (carbomethyl) anthranilic acid, 3,3′-bis (4-carboxylphenyl) propane, bis (4-carboxylphenyl) methane, 3,3′-bis (4-carboxylphenyl) ) Hexafluoropropane, 3,5-dicarboxybenzenesulfonic acid, 3,4-dicarboxybenzenesulfonic acid, and the like, and these can be used alone or in combination of two or more.

Examples of aromatic dicarboxylic acids having a phenolic hydroxyl group include 5-hydroxyisophthalic acid,
-Hydroxyisophthalic acid, 2-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 2,3-dihydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid,
And their derivatives. These can be used alone or in combination of two or more.

Further, aromatic diamines for synthesizing the aromatic polyamide resin having a phenolic hydroxyl group used in the present invention are exemplified below. For example, m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4′-diaminodiphenyl ether, 3,3 ′
-Dimethyl-4,4'-diaminodiphenyl ether,
3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4, 4′-diaminodiphenyl ether, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,
6-naphthalenediamine, benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine,
3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, m-xylylenediamine, p-xylylenediamine, 1,3-bis (methaminophenyl) -1,1, 3,3-tetramethyldisiloxane, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone, 4,4 '
-Bis (3-aminophenoxy) diphenyl sulfone,
4,4'-bis (4-aminophenoxy) diphenylsulfone, 3,3'-diaminodiphenylsulfone, 1,
3-bis (4-aminophenoxy) benzene, 4,4 '
-Bis (aminophenoxy) benzophenone, 4,4 '
-Bis (aminophenylmercapto) benzophenone,
2,2′-bis (3-aminophenyl) propane, 2,
2'-bis (4-aminophenyl) propane, 2,2 '
-Bis (4-aminophenyl) propane, 2,2'-bis (4-aminophenyl) hexafluoropropane,
2,2'-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis (4-hydroxy-3-aminophenyl) hexafluoropropane, 2,2'-bis (4- (2-trifluoromethyl-
4-aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis (4- (2-trifluoromethyl-5-aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis (4- (3- Trifluoromethyl-4-aminophenoxy) phenyl) hexafluoropropane, 2,2′-bis (4- (3-trifluoromethyl-5-aminophenoxy) phenyl) hexafluoropropane, 2,2′-bis (4 -(4-trifluoromethyl-5-aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis (4- (2-nonafluorobutyl-5-aminophenoxy) phenyl) hexafluoropropane, 2,2 ' -Bis (4- (4-nonafluorobutyl-5-aminophenoxy) phenyl) hexafluoropropane, 4,4 ' -Diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,
Examples thereof include 2,5-diaminopyridine and the like, and these can be used alone or in combination of two or more.

Examples of aromatic diamines having a phenolic hydroxyl group include bis (4-amino-3-hydroxyphenyl) methane, bis (3-amino-5-hydroxyphenyl) methane, bis (4-amino-3-) Hydroxyphenyl) ketone, 3,3′-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 3,3 ′
-Bis (3-amino-5-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-5-hydroxyphenyl) sulfone, bis (4-amino-3- Hydroxyphenyl) sulfide, bis (3-amino-5-hydroxyphenyl) sulfide, 4,4′-diamino-
3,3'-dihydroxybiphenyl, 3,3'-diamino-5,5'-dihydroxybiphenyl, 1,2'-diamino-4,6'-dihydroxybenzene, and the like. These may be used alone or in combination of two or more. Can also be used.

In the present invention, the compound represented by the following general formula (1) obtained by reacting an aromatic diamine compound having at least one alkyl group at the ortho position of the terminal aminoaryl group with an aromatic dicarboxylic acid having a phenolic hydroxyl group. Aramid resin composed of 5 to 100 mol% of the repeating structural unit shown below and 0 to 95 mol% of the repeating structural unit represented by the following general formula (2) using an aromatic dicarboxylic acid having no phenolic hydroxyl group. It is particularly preferable that the repeating structural units represented by general formulas (1) and (2) are bonded irregularly. The aramid resin has good solvent solubility and reactivity, and can improve adhesiveness and heat resistance.

Embedded image (In the above general formula, Ar represents a divalent aromatic group,
R and R ¹ represent H or an alkyl group having 1 to 4 carbon atoms, but are not H at the same time. R ² represents an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, and n represents 1 or 2)

A in the above general formulas (1) and (2)
As the divalent aromatic group represented by r, the following formulas (3) to (3)
What is shown by (5) is illustrated.

Embedded image (However, -X- is a direct _{bond, -CH 2 -, - O -} , -
S -, - CO-, or, -SO ₂ - shows a. In the case of the general formula (1), Ar has at least one —OH group. In both cases of the general formulas (1) and (2), the formulas (3) to (3)
In (5), the benzene ring and the naphthalene ring may have a substituent such as an alkyl group, a halogen, a nitro group and a sulfonic acid group. Specific examples of such aromatic dicarboxylic acids include the above-mentioned aromatic dicarboxylic acids and aromatic dicarboxylic acids having a phenolic hydroxyl group.

Examples of the aromatic diamine compound having at least one alkyl group ortho to the terminal aminoaryl group include bis (4-amino-3-methylphenyl) methane and bis (4-amino-3,5- Dimethylphenyl) methane, bis (4-amino-3-ethylphenyl) methane, bis (4-amino-3,5-diethylphenyl) methane, bis (4-amino-3ethyl-5-methylphenyl) methane, bis (4-amino-3-propylphenyl) methane, bis (4-amino-3,5-dipropylphenyl) methane, bis (4-amino-3-isopropylphenyl) methane, bis (4-amino-3,5- Diisopropylphenyl) methane, 2,2′-bis (4-
Aminophenyl) propane, 2,2′-bis (3,5-
Dimethyl-4-aminophenyl) propane, 2,2′-
Bis (3,5-diethyl-4-aminophenyl) propane, 2,2′-bis (3,5-diisopropyl-4-aminophenyl) propane, 2,2′-bis (4-aminophenyl) 1,1 , 1,3,3,3-hexafluoropropane, 2,2′-bis (3,5-dimethyl-4-aminophenyl) 1,1,1,3,3,3, -hexafluoropropane, , 2'-bis (3,5-diethyl-4
-Aminophenyl) 1,1,1,3,3,3-hexafluoropropane, 2,2′-bis (3,5-diisopropyl-4-aminophenyl) 1,1,1,3,3,
3, -hexafluoropropane and the like. These monomers may be used alone or in combination of two or more.

The aramid resin having the above structure and good solvent solubility can be suitably used for both the heat bonding type and the solvent bonding type. Further, the general formulas (1) and (2)
As the number of carbon atoms in the alkyl group of the diamine compound increases, the solubility in an alcohol solvent becomes better. Therefore, in particular, an aramid resin used for solvent bonding using an alcohol as a solvent has at least one alkyl group having at least 2 carbon atoms. It is particularly preferable to use the aromatic diamine having the above.

The aramid resin having such a phenolic hydroxyl group undergoes self-crosslinking when heated at a high temperature, and the heat resistance is dramatically improved. Further, a highly reactive phenolic hydroxyl group undergoes a condensation reaction with a methoxymethyl group of the linear polyamide resin, thereby making it possible to achieve both self-fusing property and heat resistance.

The aramid resin used in the present invention comprises:
The phosphite is added to an organic solvent containing a pyridine derivative, for example, an amide-based solvent such as N-methylpyrrolidone or dimethylacetamide. Thereafter, it can be obtained by adding a dicarboxylic acid and a diamine, and heating and stirring under an inert atmosphere such as nitrogen. After the completion of the reaction, the reaction solution may be used as it is, but when it is necessary to remove by-products and inorganic salts, the reaction solution is put into a non-solvent such as methanol to separate a produced polymer. Thereafter, purification is performed by a reprecipitation method, whereby a high-purity aramid polymer can be obtained.

In the resin composition of the present invention, it is necessary to use a linear polyamide resin in which a part of amide groups is methoxymethylated in order to improve the adhesive strength. Types of linear polyamide resin are 6-nylon, 12-nylon,
There is no limitation from general ones such as 6,6-nylon to copolymerized ones, but it is necessary to control the softening point or melting point of the resin according to the required heat resistance. In order to improve the
It is preferable to use one at 0 ° C. or higher. Further, the methoxymethylation rate can contribute to the dissolving power for alcohol, self-crosslinking between linear polyamide resins in the fusing step, and crosslinking reaction with the aramid resin. Preferably 5 to 9
It must be 0%, more preferably 10-60% methoxymethylated.

Examples of the linear polyamide resin having a softening temperature of 100 ° C. or more and a methoxymethylation ratio of about 30% include, for example, FINE RESIN FR-101, FR
-104, FR-105 (manufactured by Lead City, softening point 120-1)
30 ° C.). Since the linear polyamide resin is soluble in alcohol, it is preferably used in the case of employing a solvent bonding type, particularly an alcohol bonding type method.

The resin composition of the present invention contains at least an aramid resin as described above and a linear polyamide resin in which a part of the amide group is methoxymethylated. Or a coating dissolved or dispersed in a suitable solvent, and the shape is not particularly limited. In addition, other resin materials or additives of inorganic compounds and organic compounds can be added to the resin composition according to the purpose.

According to the bonding method of the present invention, first, a resin composition of the present invention is prepared as a coating material obtained by dissolving at least the above-mentioned aramid resin and a linear polyamide resin having a part of amide groups methoxymethylated in a solvent. . At this time, the solid content is adjusted so as to have an optimum viscosity for coating. The solvent to be used is not particularly limited as long as it can dissolve the resin composition, but N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DM
It is preferable to use a high-boiling solvent such as F), m-cresol, benzyl alcohol or the like, since the coating has good stability over time and the surface state of the coating after desolvation becomes good. When the linear polyamide resin is soluble in alcohol, a coating method using the above solvent in combination with alcohols is also possible. After the coating material is applied to the surface of the adherend A, the solvent is removed using a hot air drier or the like, and a film is formed on the adherend A. The thickness of the resin film is adjusted according to the thickness of the target adhesive layer, but is generally in the range of 5 to 200 μm. In this case, it is also a preferable method to perform the coating twice or more times in order to uniformly form the coating to a desired thickness. It is desirable that the residual solvent in the film after the solvent is removed is as small as possible in order to eliminate the blocking property of the film after the film is formed.
wt% or less. More preferably, it is 1 wt% or less.

Next, in the case of heat bonding, as a first method of the present invention, the resin film is heated, and the adherend B is superimposed on the heated resin film surface. In the second method, after the adherend B is first overlaid on the resin coating surface, the adherend A
The heating is performed from the side or the adherend B side or the whole. Here, when the adherend A on which the resin film is formed is used as the adherend B, that is, when the adherends A are bonded to each other, more excellent adhesive strength is achieved when the adherends are combined with the resin film side inward. You. The heating conditions are as follows: a given temperature is applied for a given time in a heating furnace while applying a fixed load to the bonding surface, and bonding is performed. Here, the temperature is preferably, for example, a temperature equal to or higher than the softening point of the resin, and is about 50 to 300 ° C., and the time is appropriately set depending on the resin composition and the material of the adherend, for example, 30 seconds. From the above, it is preferable that the time is at most about 5 hours in consideration of work efficiency and the like.

Further, the third and fourth embodiments in the case of solvent bonding are used.
In the method of (1), after applying a solvent capable of dissolving the coating to the resin coating by a spray method or a dipping method or the like, the adherend B is superimposed on the resin coating surface, and in the case of the third bonding method of the present invention, Air dry at room temperature and adhere. Further, in the case of the fourth bonding method, after the adherends B are overlaid, they are further heated and dried by hot air or the like and bonded. These third
Also, in the fourth method, when the adherend A having a resin film formed thereon is used as the adherend B, that is, when the adherents A are bonded to each other, a better adhesive strength can be obtained by joining the resin film surfaces together. It is preferable because it is possible. In the case of an alcohol-soluble resin film, the coating can be carried out using an alcohol-based solvent such as methanol or ethanol.

The material and shape of the adherend A and the adherend B in the bonding method of the present invention are not particularly limited as long as they are solid. For example, copper, iron, aluminum, zinc, titanium, etc. Metals and their compounds, glass, ceramics, silicon compounds, inorganic materials such as stainless steel, polyimide, polyamide, polyester, polyurethane,
Examples include films and molded articles of polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, epoxy resin, silicone resin, and the like, and fibrous materials such as paper, synthetic paper, woven fabric, nonwoven fabric, and the like. Adhesion with each other or with different types may be used. When the adherend is a conductor, the resin composition of the present invention may be applied and adhered on the adherent as it is, but in order to achieve better insulation after the adhesion, other It is also effective to form a resin film via an insulating layer such as resin. As the insulating layer in this case, general oil-based enamel paint, formal paint, polyester paint, polyurethane paint, polyimide paint, polyamideimide paint, etc. can be used, but in the field where heat resistance is required, polyimide paint or polyamideimide is used. It is preferable to use a paint.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
In the examples, parts are parts by weight. Synthesis Example 1 300 ml capacity equipped with a mechanical stirrer, reflux condenser, thermometer, calcium chloride tube, and nitrogen inlet tube
11.30 g (40 mmo) of bis (4-amino-3-ethyl-5-methylphenyl) methane (manufactured by Ihara Chemical, trade name: Cure Hard MED) in a three-necked round bottom flask
l), 5-hydroxyisophthalic acid (Nippon Kayaku Co., Ltd.)
7.28 g (40.0 mmol), 2.02 g of calcium chloride as a stabilizer, 0.66 g of lithium chloride, and 120 g of N-methyl-2-pyrrolidone as a condensing agent;
Pyridine 4.0 g, triphenyl phosphite 24.82 g
(80.0 mmol). Then, the flask was heated to 120 ° C. in an oil bath under a nitrogen atmosphere for 4 hours.
Stirred for hours. After stirring, the reaction solution was cooled to room temperature, and dropped into 4 liters of a solution (water / methanol = 1/1) to precipitate a resin. This was filtered by suction, washed twice with a solution (water / methanol = 9/1), and dried to obtain an aramid resin having a phenolic hydroxyl group in a yield of 98%. The intrinsic viscosity (η) of the obtained aramid resin is 0.63 dl / g
(Solvent: N, N-dimethylacetamide, concentration: 0.5
g / dl, temperature: 30 ° C.) and was insoluble in alcohol solvents.

Synthesis Example 2 11.30 g (40 mmol) of bis (4-amino-3-ethyl-5-methylphenyl) methane (manufactured by Ihara Chemical, trade name: Cure Hard MED) of Example 1 was added to bis (4-amino) -3,5-diethylphenyl) methane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYABOND C-300)
S) Synthesis was performed in the same manner as in Example 1 except that the amount was changed to 12.42 g (40.0 mmol) to obtain an intended aramid resin having a phenolic hydroxyl group. The intrinsic viscosity (η) of the obtained aramid resin having a phenolic hydroxyl group is
0.60 dl / g (solvent: N, N-dimethylacetamide, concentration: 0.5 g / dl, temperature: 30 ° C.), which was soluble in alcohol solvents.

Synthesis Example 3 11.30 g (40 mmol) of bis (4-amino-3-ethyl-5-methylphenyl) methane (manufactured by Ihara Chemical, trade name: Cure Hard MED) of Example 1 was added to bis (4-amino). 14.64 g of 3,5-diisopropylphenyl) methane (manufactured by Nippon Kayaku Co., Ltd., trade name: C-400)
(40 mmol) to obtain an intended aramid resin having a phenolic hydroxyl group in the same manner as in Example 1 except that the amount was changed to 40 mmol. The intrinsic viscosity (η) of the obtained aramid resin having a phenolic hydroxyl group is 0.54 dl / g (solvent: N, N-dimethylacetamide, concentration: 0.5 g / g).
dl, temperature: 30 ° C) and was soluble in alcoholic solvents.

Synthesis Example 4 11.30 g (40 mmol) of bis (4-amino-3-ethyl-5-methylphenyl) methane (manufactured by Ihara Chemical, trade name: Cure Hard MED) of Example 1 was added to 3,
8.01 g of 4'-diaminodiphenyl ether (trade name: 3,4'-DAPE, manufactured by Mitsui Chemicals, Inc., 40 mmo)
Synthesis was performed in the same manner as in Example 1 except for changing to l) to obtain the desired aramid resin having a phenolic hydroxyl group.
The intrinsic viscosity (η) of the obtained aramid resin having a phenolic hydroxyl group is 0.60 dl / g (solvent: N, N-dimethylacetamide, concentration: 0.5 g / dl, temperature: 3
0 ° C.) and was insoluble in alcohol solvents.

Synthesis Example 5 11.30 g (40 mmol) of bis (4-amino-3-ethyl-5-methylphenyl) methane (manufactured by Ihara Chemical, trade name: Cure Hard MED) of Example 1 was added to bis (4-amino -3,5-diethylphenyl) methane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYABOND C-300)
S) Synthesis was carried out in the same manner as in Example 1 except that 10.87 g (35.0 mmol) and 0.83 g of isophthalic acid (manufactured by AGI) were obtained to obtain an intended aramid resin having a phenolic hydroxyl group. The intrinsic viscosity (η) of the obtained phenolic hydroxyl group-containing aramid resin is 0.61 dl /
g (solvent: N, N-dimethylacetamide, concentration: 0.
5 g / dl, temperature: 30 ° C.) and was soluble in alcoholic solvents.

Example 1 Alcohol-soluble aramid resin 50 obtained in Synthesis Example 2
Parts and 50 parts of a linear polyamide resin (trade name: FR-101, manufactured by Lead City Co., Ltd.) having a methoxymethylation ratio of 30% were mixed with a mixed solvent 300 of methanol / N, N-dimethylformamide = 1/1 (weight ratio). And melted at room temperature to obtain a resin composition of the present invention. Example 2 Alcohol-soluble aramid resin 30 obtained in Synthesis Example 2
Parts and 70 parts of a linear polyamide resin (trade name: FR-101, manufactured by Lead City Co., Ltd., having a methoxymethylation ratio of 30%) were mixed with a mixed solvent 300 of methanol / N, N-dimethylformamide = 1/1 (weight ratio). And melted at room temperature to obtain a resin composition of the present invention.

Example 3 Alcohol-soluble aramid resin 20 obtained in Synthesis Example 2
Parts and 80 parts of a linear polyamide resin (trade name: FR-101, manufactured by Lead City Co., Ltd., having a methoxymethylation ratio of 30%) were mixed with a mixed solvent 300 of methanol / N, N-dimethylformamide = 1/1 (weight ratio). And melted at room temperature to obtain a resin composition of the present invention. Example 4 Methanol / N, N-dimethyl was added to 30 parts of the aramid resin obtained in Synthesis Example 1 and 70 parts of a linear polyamide resin (trade name: FR-104, manufactured by Lead City Co., Ltd.) having a methoxymethylation ratio of 30%. Formamide = 1/1 (weight ratio) mixed solvent 30
0 parts were added and dissolved at room temperature to obtain a resin composition of the present invention.

Example 5 Alcohol-soluble aramid resin 30 obtained in Synthesis Example 3
Parts and 70 parts of a linear polyamide resin (trade name: FR-105, manufactured by Lead City Co., Ltd., having a methoxymethylation rate of 30%) were mixed with a mixed solvent 300 of methanol / N, N-dimethylformamide = 1/1 (weight ratio). And melted at room temperature to obtain a resin composition of the present invention. Example 6 Methanol / N, N-dimethyl was added to 30 parts of the aramid resin obtained in Synthesis Example 4 and 70 parts of a linear polyamide resin having a methoxymethylation ratio of 30% (trade name: FR-105, manufactured by Lead City Co., Ltd.). Formamide = 1/1 (weight ratio) mixed solvent 30
0 parts were added and dissolved at room temperature to obtain a resin composition of the present invention. Example 7 Alcohol-soluble aramid resin 30 obtained in Synthesis Example 5
Parts and 70 parts of a linear polyamide resin (trade name: FR-101, manufactured by Lead City Co., Ltd., having a methoxymethylation ratio of 30%) were mixed with a mixed solvent 300 of methanol / N, N-dimethylformamide = 1/1 (weight ratio). And melted at room temperature to obtain a resin composition of the present invention.

Comparative Example 1 Alcohol-soluble aramid resin 10 obtained in Synthesis Example 2
In 0 parts, methanol / N, N-dimethylformamide =
300 parts of a 1/1 (weight ratio) mixed solvent was added and dissolved at room temperature to obtain a resin composition for comparison. Comparative Example 2 Alcohol-soluble aramid resin 70 obtained in Synthesis Example 2
Part and alcohol-soluble thermoplastic polyamide copolymer (B
300 parts of a mixed solvent of methanol / N, N-dimethylformamide = 1/1 (weight ratio) was added to 30 parts of ASF, trade name: Ultramid 1C, a linear polyamide resin having a methoxymethylation ratio of 0%. At room temperature to obtain a comparative resin composition.

Comparative Example 3 Methanol / N, N-dimethylformamide = 1/1 (weight ratio) was added to 100 parts of a linear polyamide resin having a methoxymethylation ratio of 30% (trade name: FR-105, manufactured by Lead City Co., Ltd.). Was added at room temperature, and a resin composition for comparison was obtained. Comparative Example 4 70 parts of an aromatic polyamide resin having no phenolic hydroxyl group synthesized from 3,4'-diaminodiphenyl ether and isophthalic acid and a linear polyamide resin having a methoxymethylation ratio of 30% (trade name, manufactured by Lead City Co., Ltd.) FR-105) 30
In the part, methanol / N, N-dimethylformamide = 1
300 parts by weight of a 1: 1 (weight ratio) mixed solvent was added and dissolved at room temperature to obtain a resin composition for comparison.

Next, an adhesion test was performed on the resin compositions of the above Examples and Comparative Examples. 1. Preparation of test piece 1) Test piece (1) Each of the resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 was 3
It is applied to a thickness of 10 μm on a copper foil of 5 μm (corresponding to the adherend A), and is applied at 200 ° C. for 1 min. The solvent was removed in a hot air drier so that the solvent amount was 1 wt% or less, and a resin film was formed on the copper foil. This resin-coated copper foil was cut into a size of 5 cm × 1 cm to obtain a sample for an adhesion test.

2) Test piece (2) N-methyl-2-pyrrolidone 450 was added to 100 parts of a polar solvent-soluble aromatic polyamideimide resin synthesized from 4,4'-diaminodiphenyl ether and trimellitic anhydride.
Was added and dissolved. The obtained polyamideimide paint was applied on a 35 μm copper foil to a thickness of 20 μm,
° C, 2 min. The solvent was removed in a hot air drier so that the solvent amount was 1 wt% or less, and a film was formed on the copper foil. The resin composition of Example 2 was applied in a thickness of 10 μm to the polyamideimide coating surface of the copper foil (corresponding to the adherend material A) on which the coating was formed, and was applied at 200 ° C. for 1 min. The solvent was removed in a hot air drier so that the amount of the solvent was 1 wt% or less, to form a film containing an alcohol-soluble aramid resin. This resin-coated copper foil was cut into a size of 5 cm × 1 cm to obtain a sample for an adhesion test.

2. Adhesion of test pieces 1) Thermal bonding method Each sample prepared above is overlapped with the resin coating side inside, and a desktop test press (manufactured by Shindo Metal Industry)
And set to 10 kg / cm ² using 18
It was pressed at 0 ° C. for 30 minutes for bonding. 2) Solvent bonding method Each sample prepared as described above was immersed in a solvent described in Table 2 for about 1 second, and the samples were overlapped with the resin coating side inside, and the weight was adjusted to 5 kg / cm ^2. The plate was placed on a hot air dryer and left at 180 ° C. for 1 hour for bonding.

3. Test of Adhesive Strength Using a Tensilon UCT-500 (manufactured by Orientec), the above-mentioned bonded sample was subjected to the following conditions under the following conditions.
The 80 degree peel strength was measured. The average value of the five measurement data was determined and defined as the adhesive strength. Head speed: 5 mm / min. Measurement temperature: The adhesive strength at 25 ° C. was A, and the adhesive strength at 180 ° C. was B. Further, the holding ratio of the adhesive strength in an environment of 180 ° C. was determined by the following formula. Adhesive strength retention (%) = B ÷ A × 100

The results of each of the examples and comparative examples obtained by the above tests are as shown in Tables 1 and 2.

[Table 1]

[Table 2]

As is clear from the results shown in Tables 1 and 2, the resin compositions of Examples 1 to 7 of the present invention can obtain sufficient adhesive strength at room temperature by any of the thermal bonding and the solvent bonding.
Even at a high temperature of 180 ° C., the retention of the adhesive strength was 80% or more, indicating good adhesiveness. Furthermore, in the resin compositions of Examples 1 to 3, 5 and 7, solvent bonding with alcohol is possible, which can greatly contribute to improvement of the working environment. On the other hand, although the resin compositions of Comparative Examples 2 to 4 had sufficient adhesiveness at room temperature, the adhesive strength at a high temperature of 180 ° C. was low and the retention was 70% or less, which was insufficient. Further, although the resin composition of Comparative Example 1 had a high retention, the adhesive strength was insufficient, and had a practical problem.

[0044]

As described above, when a resin composition containing an aromatic polyamide resin having at least a phenolic hydroxyl group and a linear polyamide resin in which a part of the amide group is methoxymethylated is used, good adhesive strength is obtained. It is possible to form an adhesive layer having excellent insulation properties and heat resistance with little decrease in adhesive strength even in a high temperature environment. In addition, by using the bonding method of bonding after covering the adherend, it can be applied to bonding of components such as electric or electronic equipment, and has effects such as expansion of the operating temperature environment of the equipment and improvement of reliability. .

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CL012 CL032 CL061 EC026 GJ01 4J040 EG002 EG012 EG021 EG022 GA03 GA05 GA08 JA02 LA08 LA09 MB14 NA19 5G305 AA11 AB24 AB34 BA09 CA20 CA45 CA55 CB10 DA22 DA24

Claims (10)

[Claims] 1. A resin composition containing at least an aromatic polyamide resin having a phenolic hydroxyl group and a linear polyamide resin in which a part of an amide group is methoxymethylated. 2. A phenolic hydroxyl group comprising at least 5 to 100 mol% of a repeating structural unit represented by the following general formula (1) and 0 to 95 mol% of a repeating structural unit represented by the following general formula (2): A resin composition comprising: an aromatic polyamide resin having the formula: and a linear polyamide resin having a part of amide groups methoxymethylated. Embedded image (In the above general formula, Ar represents a divalent aromatic group,
R and R ¹ represent H or an alkyl group having 1 to 4 carbon atoms, but are not H at the same time. R ² represents an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, and n represents 1 or 2) 3. The resin composition according to claim 1, wherein the aromatic polyamide resin having a phenolic hydroxyl group and the linear polyamide resin obtained by partially methoxymethylating an amide group are alcohol-soluble. 4. A step of applying and drying the resin composition according to claim 1 on the surface of the adherend A to form a resin film on the surface of the adherend A; and heating the surface of the resin film; Adhering the adherend B to the heated resin film surface by superimposing the adherend B on the heated resin film surface. 5. A step of applying and drying the resin composition according to claim 1 on the surface of the adherend A to form a resin film on the surface of the adherend A; and overlaying the adherend B on the surface of the resin film. Combining step; and heating the resin film to form an adherend A and an adherend B
Bonding; a bonding method comprising: 6. A step of applying and drying the resin composition according to claim 1 on the surface of the adherend A to form a resin film on the surface of the adherend A; and dissolving the resin film on the surface of the resin film. A bonding method, comprising: a step of applying a solvent; and a step of laminating and bonding the adherend B to the resin coating surface. 7. A step of applying and drying the resin composition according to claim 1 on the surface of the adherend A to form a resin film on the surface of the adherend A; dissolving the resin film on the surface of the resin film. A bonding method, comprising: a step of applying a solvent; and a step of heating and bonding after superposing the adherend B on the resin film surface. 8. The bonding method according to claim 6, wherein an alcohol solvent is used as the solvent. 9. The bonding method according to claim 4, wherein the adherend A is a conductor and a resin film is formed directly or via another insulating material. 10. The method according to claim 4, wherein the adherend B is the same as the adherend A on which the resin film is formed, and the resin film surfaces are overlapped and bonded. Bonding method.