JPWO2009028170A1 - Thermosetting resin composition and cured product thereof - Google Patents

Abstract

The present invention provides (i) a reactive hydroxyl group-containing polyamide resin, (ii) at least one epoxy selected from the group consisting of an epoxy resin having a polycondensate skeleton of dicyclopentadiene and phenol, a phenol aralkyl skeleton, and a biphenol aralkyl skeleton. It relates to a thermosetting resin composition comprising a resin and (iii) at least one epoxy resin curing agent selected from the group consisting of phenolic compounds having the same skeleton as the epoxy resin, and is cured at a low heat treatment temperature. Moreover, the cured product has high heat resistance and high adhesive strength in a wide temperature range. Therefore, it is useful as an adhesive used for electrical and electronic materials such as the resin composition, flexible wiring board, and laminate, and an insulating protective material.

Description

  The present invention relates to a thermosetting resin composition suitable for applications such as a semiconductor encapsulant, a flexible wiring board, a laminate, and an insulating protective material used for electrical and electronic materials, and the thermosetting suitable for those applications. A film comprising a resin composition, an adhesive comprising the thermosetting resin composition, and a cured product thereof, wherein the thermosetting resin composition and a film or adhesive comprising the same are heat resistant, adhesive, And a cured product having excellent dielectric properties.

  Recent developments in the electric / electronic field have been remarkable, and in the fields of flexible wiring boards and laminates, improvements in heat resistance, reliability, thickness reduction, precision workability, flexibility and the like are required. At present, in order to meet these requirements, polyimide resin, polyamide resin, or the like is frequently used as a constituent material for flexible wiring boards and laminated boards. In general, a polyimide resin or a polyamide resin has high heat resistance and flexibility, but when applied to the above application as an adhesive or a film, heat treatment at a high temperature of about 300 ° C. is required at the time of curing. In order to facilitate direct application to electrical / electronic components, reduction of the heat treatment temperature is desired. Further, cured products of these resin compositions are required to further improve various properties such as flame retardancy, high heat resistance, high adhesiveness, reliability during heat, low dielectric constant, and fracture toughness. Many proposals have been made to solve these problems. For example, Patent Documents 1 and 2 disclose a heat-resistant film including a polyimide resin, an epoxy resin, and an epoxy resin curing agent, an adhesive, a resin composition, and the like. Although those disclosed in the document achieve the purpose of lowering the processing temperature, the problem that the heat resistance of the cured product is lowered has not been solved.

JP-A-8-27430 JP 2006-348086 A

  The present invention relates to a thermosetting resin composition capable of obtaining a cured product having a low heat treatment temperature during curing, high heat resistance, and high adhesive strength in a wide temperature range from room temperature to high temperature, and the cured product thereof. Is to provide.

As a result of intensive studies on the above problems, the present inventors have been able to cure a thermosetting resin composition containing a polyamide resin, an epoxy resin having a specific skeleton, and an epoxy resin curing agent at a low heat treatment temperature. The cured product was found to have high heat resistance and high adhesive strength over a wide temperature range, thereby completing the present invention.
That is, the present invention
(1) A reactive hydroxyl group-containing polyamide resin obtained by subjecting 3,4'-diaminodiphenyl ether, isophthalic acid and 5-hydroxyisophthalic acid to a dehydration condensation reaction,
The following formula (2), formula (3) or formula (4)

(In the formula, n is an average value and represents a number exceeding 0 and 10 or less, and G represents a glycidyl group)
And at least one epoxy resin selected from the group consisting of compounds represented by formula (5), formula (6) or formula (7):

(In the formula, n is an average value and represents a number exceeding 0 and not exceeding 10)
A thermosetting resin composition comprising at least one epoxy resin curing agent selected from the group consisting of compounds represented by:
(2) The content of at least one epoxy resin selected from the group consisting of epoxy resins represented by formula (2), formula (3) and formula (4) is a reactive hydroxyl group-containing polyamide resin, epoxy resin and epoxy The thermosetting resin composition according to (1), which is 2 to 50% by mass with respect to the total mass of the resin curing agent.
(3) A film comprising the thermosetting resin composition according to (1) or (2) above,
(4) A flexible wiring board to which the thermosetting resin composition according to (1) or (2) is applied,
(5) A laminated board to which the thermosetting resin composition according to (1) or (2) is applied,
(6) Insulating protective material to which the thermosetting resin composition according to (1) or (2) is applied,
(7) An adhesive comprising the thermosetting resin composition according to (1) or (2) above,
(8) A cured product of the thermosetting resin composition according to (1) or (2) above,

(9) The thermosetting resin composition according to the above (1) or (2), comprising at least one of the epoxy resin represented by formula (2) or the epoxy resin curing agent represented by formula (5) ,
(10) Following (a) or (b)
(A) a combination of the epoxy resin represented by formula (2) and at least one of the epoxy resin curing agents represented by formula (6) or formula (7), or (b) in formula (5) A combination of the epoxy resin curing agent represented and at least one of the epoxy resins represented by formula (3) or (4),
The thermosetting resin composition according to any one of the above (1), (2), or (9), comprising any combination of
(11) The thermosetting resin composition according to any one of (1), (2), (9) and (10) above, wherein both ends of the reactive hydroxyl group-containing polyamide resin are amino groups,
(12) (i) a reactive hydroxyl group-containing polyamide resin, (ii) at least one epoxy resin selected from the group consisting of compounds represented by formula (2), formula (3) and formula (4); iii) The total amount of at least one epoxy resin curing agent selected from the group consisting of compounds represented by formula (5), formula (6) and formula (7) is the resin component in the thermosetting resin composition. The thermosetting resin composition according to any one of (1), (2), and (9) to (11), which is 85 to 100% by mass relative to the total amount,
(13) The thermosetting resin composition according to any one of (1), (2), and (9) to (12), further containing a curing accelerator,
(14) The thermosetting resin composition according to (13), wherein the curing accelerator is an imidazole compound,
(15) A thermosetting resin composition solution comprising the thermosetting resin composition according to any one of (1), (2), and (9) to (14), and a solvent,
(16) The resin composition according to the above (15), wherein the solvent is dimethyl sulfoxide.
(17) In at least one epoxy resin selected from the group consisting of epoxy resins represented by formula (2), formula (3) and formula (4) in the thermosetting resin composition, or other epoxy When resin is used in combination, at least one epoxy resin curing agent selected from the group consisting of compounds represented by formula (5), formula (6) and formula (7) with respect to 1 equivalent of epoxy group in the total amount of both And the average active hydrogen amount in the total amount of the reactive hydroxyl group-containing polyamide resin, or when using other epoxy resin curing agents in combination, the total amount of epoxy resin curing agents including other epoxy resin curing agents and reactive hydroxyl group content The thermosetting resin according to any one of (1), (2), and (9) to (16) above, wherein an average active hydrogen amount in a total amount with the polyamide resin is 0.6 to 1.2 equivalents. Composition,
(18) A flexible wiring board, a laminate or an insulating protective material to which the thermosetting resin composition according to any one of (9) to (16) is applied, or any of (9) to (16) An adhesive comprising the thermosetting resin composition according to claim 1;
It is about.

  The thermosetting resin composition of the present invention and the film comprising the resin composition can be cured at a low heat treatment temperature of about 160 to 200 ° C., and the cured product has high heat resistance and a wide temperature range. High adhesive strength. Therefore, the resin composition or a film made of the resin composition is useful as an adhesive or an insulating protective material used for electrical and electronic materials such as flexible wiring boards and laminated boards.

The present invention will be described in detail below.
Reactive hydrogen group-containing polyamide obtained by subjecting 3,4'-diaminodiphenyl ether (A), isophthalic acid (B) and 5-hydroxyisophthalic acid (C) to dehydration condensation reaction Resin (hereinafter referred to as “reactive polyamide resin”).
A preferred synthesis method of the reactive polyamide resin used in the present invention is described in Synthesis Example 1 described later. The terminal structure of the reactive polyamide resin obtained by synthesis depends on the molar ratio of the diamine component (A) used in the synthesis and the total of the isophthalic acid components (B) and (C). Specifically, when the number of moles of the components (A), (B) and (C) used in the synthesis is a, b and c, respectively, if a> b + c, the end of the reactive polyamide resin becomes an amino group. , A <b + c, the terminal is a carboxyl group. At this time, the value of a / (b + c) is preferably in the range of 0.5 to 2, and more preferably in the range of 0.7 to 1.5. Since those having a carboxyl group at the end are inferior in storage stability when formed into a composition, the reactive polyamide resin used in the thermosetting resin composition of the present invention preferably has an amino group at the end. That is, the value of a / (b + c) is greater than 1 and preferably 1.5 or less, more preferably greater than 1 and 1.2 or less, and even more preferably greater than 1 and 1.15 or less. In addition, as for the use ratio of the component (B) and the component (C), since the heat resistance after curing tends to improve and the flexibility tends to decrease as the amount of the component (C) having a hydroxyl group increases, both characteristics From the balance, the value of c / (b + c) is in the range of 0.01 to 0.5, more preferably in the range of 0.01 to 0.1, and in some cases the range of 0.02 to 0.5 is preferred. .

The reactive polyamide resin is presumed to have a structure represented by the following formula (1).
Formula (1)

(In the formula, the ratio of n and m corresponds to the ratio of b and c where the number of moles of (B) isophthalic acid and (C) 5-hydroxyisophthalic acid used in the synthesis is b and c, respectively. n + m is preferably in the range of 10-60)
When the value of n + m is smaller than 10, the molecular weight of the reactive polyamide resin is too small, which may cause a decrease in heat resistance after curing. When it is larger than 60, the viscosity of the polyamide resin is high at the time of synthesis. If it becomes too much, handling may be difficult. The more preferable range of n + m is 40 to 60, and more preferably 45 to 55.

  The amount of the reactive polyamide resin used in the thermosetting resin composition of the present invention is such that (i) the reactive polyamide resin, (ii) the epoxy resin, and (iii) the epoxy resin curing agent in the thermosetting resin composition. 40-95 mass% is preferable with respect to the total mass, 40-70 mass% is more preferable, More preferably, it is 40-65 mass%.

  The thermosetting resin composition of the present invention contains one or more epoxy resins selected from the compounds represented by formula (2), formula (3) or formula (4).

  The epoxy resin represented by the formula (2) can be synthesized by dehydrochlorinating a phenol compound that is a polymer of phenol and dicyclopentadiene and epichlorohydrin. As a commercially available product, XD-1000 (manufactured by Nippon Kayaku Co., Ltd.) and the like are available. However, if the value of n in formula (2) exceeds 0 and is 10 or less, it is limited to this. is not. Preferred n is an average value of about 1 to 8, more preferably about 2 to 5.

  The epoxy resin represented by the formula (3) can be synthesized by dehydrochlorinating a phenol aralkyl compound, which is a reaction product of phenol and dialkoxymethylbenzene, and epichlorohydrin. As this phenol aralkyl resin, SYROC 3L (manufactured by Mitsui Chemicals, Inc.) is available as a commercial product. Therefore, as described in Synthesis Example 2 described later, it is synthesized by an epoxidation reaction between this and epichlorohydrin. However, it is not limited to this as long as the value of n in the formula (3) exceeds 0 and is 10 or less. Preferred n is an average value, which is about 1 to 8, more preferably about 3 to 8, and further preferably about 4 to 6.

  The epoxy resin represented by the formula (4) can be synthesized by dehydrochlorinating a phenol aralkyl compound, which is a reaction product of phenol and bisalkoxymethylbenzene, and epichlorohydrin. NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) is available as a commercial product, but is limited to this if the value of n in formula (3) exceeds 0 and is 10 or less. is not. Preferable n is an average value and is about 1-6, More preferably, it is about 1-4, More preferably, it is about 1-3.

The usage-amount of 1 or more types of epoxy resins chosen from the compound represented by Formula (2), Formula (3), or Formula (4) in the thermosetting resin composition of this invention is a thermosetting resin composition. 2-50% by mass, preferably 15-50% by mass, more preferably about 20-40% by mass, and still more preferably 25-50% by mass with respect to the total mass of the reactive polyamide resin, epoxy resin and epoxy resin curing agent therein. About 40% by mass, most preferably about 25-35% by mass.
In addition, the value of n in Formula (2), Formula (3), and Formula (4) should be calculated from the value of the number average molecular weight determined by gel permeation chromatography (GPC) measurement of each epoxy resin. I can do it.

  The thermosetting resin composition of the present invention contains one or more epoxy resin curing agents selected from the compounds represented by formula (5), formula (6), or formula (7).

The epoxy resin curing agent represented by the formula (5) can be synthesized by polymerization reaction of phenol and dicyclopentadiene as described in Synthesis Example 3 described later. In the polymerization reaction, the value of n in the formula (5) can be controlled by increasing or decreasing the amount of phenol used for dicyclopentadiene.
The value of n in the formula (5) is usually more than 0 and 10 or less. For example, with respect to cyclopentadiene, phenol is used in a molar ratio of about 4 to 6 times, for example, at a temperature of about 40 to 80 ° C., usually for about 0.5 to 2 hours until the reaction is completed. Can be obtained.

  The epoxy resin curing agent represented by the formula (6) can be synthesized by reacting phenol with dialkoxymethylbenzene or the like. As a commercial product, XYLOCK 3L (made by Mitsui Chemicals, Inc.) and the like can be obtained, but it is not limited to this as long as the value of n in formula (6) exceeds 0 and is 10 or less. . Preferred n is an average value, which is about 1 to 8, more preferably about 2 to 5.

  The epoxy resin curing agent represented by the formula (7) can be synthesized by reacting phenol with bisalkoxymethylbenzene or the like. GPH-65 (manufactured by Nippon Kayaku Co., Ltd.) is available as a commercial product, but is limited to this if the value of n in formula (7) exceeds 0 and is 10 or less. is not. Preferred n is an average value, which is about 1 to 6, more preferably about 1 to 4, and still more preferably about 1 to 2.

In addition to the epoxy resins represented by the above formula (2), formula (3) and formula (4), other epoxy resins may be used in combination with the thermosetting resin composition of the present invention as long as the properties are not impaired. I can do it. The epoxy resin that can be used in combination is not particularly limited. For example, novolak type epoxy resin, phenol aralkyl type epoxy resin, polyphenol type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, halogenated phenol epoxy resin, glycidylamine Epoxy resin, glycidyl ester epoxy resin and the like. Two or more of these epoxy resins can be used in combination.
The amount of the other epoxy resin that can be used in combination is preferably 20% by mass or less based on the total mass of the epoxy resin component in the thermosetting resin composition.
In addition, the value of n in Formula (5), Formula (6), and Formula (7) is computed from the value of the number average molecular weight calculated | required by the measurement of the gel permeation chromatography (GPC) of each epoxy resin hardening | curing agent. I can do it.

  In the thermosetting resin composition of the present invention, in addition to the epoxy resin curing agent represented by the above formula (5), formula (6) and formula (7), various epoxy resin curing agents can be used as long as the properties are not impaired. Can be used together. The curing agent that can be used in combination is not particularly limited. For example, a phenolic curing agent such as a phenol novolac resin, a phenol aralkyl resin, or a polyphenol resin, a modified phenol curing agent such as a naphthol-modified phenol novolak or dicyclopentadiene-modified polyphenol, or phthalate. Examples include acid anhydride type curing agents such as acid anhydride and trimellitic acid anhydride, and amine type curing agents such as diaminodiphenylmethane and dicyandiamide. These curing agents may be used in combination of two or more.

The amount of the epoxy resin curing agent used in the thermosetting resin composition of the present invention is at least selected from the group consisting of compounds represented by formula (2), formula (3) and formula (4) in the composition. When one type of epoxy resin and another type of epoxy resin that can be used in combination are used in combination, the formula (5), formula (6), and formula (7) ) In the total amount of at least one epoxy resin curing agent selected from the group consisting of compounds represented by the above and the reactive polyamide resin, or when using another epoxy resin curing agent in combination, other epoxy resin curing agents It is preferable to use an amount in which the average active hydrogen amount in the total amount of the epoxy resin curing agent including the reactive hydroxyl group-containing polyamide resin is in the range of 0.2 to 1.5 equivalents, particularly 0.6 to 1.2 equivalent range It is preferably used. The active hydrogen in the reactive polyamide resin here is hydrogen having a hydroxyl group and hydrogen having an amino group.
Moreover, the usage-amount of the hardening | curing agent which can be used together described in Paragraph 0028 has the preferable amount which occupies 20 mass% or less in the total mass of the epoxy resin hardening | curing agent component in a thermosetting resin composition.

The thermosetting resin composition in the present invention is (i) a reactive polyamide resin, (ii) at least one selected from the group consisting of compounds represented by formula (2), formula (3) and formula (4). And (iii) at least one epoxy resin curing agent selected from the group consisting of compounds represented by formula (5), formula (6) and formula (7) (hereinafter referred to as three resin components) As long as the resin component such as an epoxy resin or an epoxy curing agent not included in the resin component achieves the effects of the present invention. In general, the content is preferably about 0 to 15% by mass, more preferably 0 to 10% by mass, based on the total amount of resin components in the thermosetting resin composition of the present invention. It is a grade, More preferably, it is 0-5 quality The resin component content is preferably 85 to 100% by mass, more preferably 90 to 100%, based on the total amount of the resin component in the thermosetting resin composition. It is 95 mass%, More preferably, it is 95-100 mass%, Most preferably, it is 100%.
As the reactive hydroxyl group-containing polyamide resin, in addition to the reactive polyamide used in the present invention, a reactive hydroxyl group-containing rubber-modified polyamide resin and the like are also known, but it is preferable not to include them in the present invention.

The thermosetting resin composition of the present invention preferably contains at least one of an epoxy resin represented by formula (2) or an epoxy resin curing agent represented by formula (5). When the epoxy resin represented by the formula (2) is included, the content thereof may be the content described in the section of the epoxy resin, preferably about 20 to 40% by mass with respect to the total amount of the resin component. Preferably it is about 25-40 mass%, More preferably, it is about 25-35 mass%. Further, when the epoxy resin curing agent represented by the formula (5) is included, the content thereof may be the content described in the section of the epoxy resin curing agent, and usually from the total amount of the present resin component, The balance obtained by subtracting the content of the reactive polyamide resin (i) and the epoxy resin (ii) is preferably about 10 to 30% by mass, more preferably about 15 to 30% by mass, and still more preferably 15 to 25%. It is about mass%. In some cases, both the epoxy resin represented by the formula (2) and the epoxy resin curing agent represented by the formula (5) may be used in combination, and in that case, the total content of both is about 20 to 40% by mass. Thus, the shortage of each component is supplemented with another epoxy resin or other epoxy resin curing agent as an essential component in the present invention, and the epoxy resin content is about 20 to 40% by mass or more. Preferably it is about 25-40 mass%, More preferably, it is about 25-35 mass%, The epoxy resin hardening | curing agent content is preferably about 10-30 mass%, More preferably, it is about 15-30 mass%, More preferably, it is 15-25 What is necessary is just to use each together so that it may become about the mass%.
The content of the reactive polyamide resin (i) is about 30 to 70% by mass, more preferably about 40 to 70% by mass, and still more preferably about 40 to 65% by mass with respect to the total amount of the resin component.

  The thermosetting resin composition of the present invention can be used by adding additives other than the resin component, for example, a curing accelerator, a filler, an ion scavenger and the like, if necessary.

The curing accelerator is not particularly limited as long as it accelerates the reaction between the epoxy resin and the active hydrogen group-containing polyamide resin or the curing agent. For example, organic phosphorus compounds, imidazole compounds, tertiary amines, sulfonium salts, quaternary ammonium salts and the like are used. These curing accelerators are appropriately selected depending on the type of epoxy resin and curing agent used, molding conditions, required characteristics, and the like. In the present invention, an imidazole compound is preferred. For example, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole (2PHZ), 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. And 2-phenyl-4,5-dihydroxymethylimidazole is more preferable.
The thermosetting resin composition of the present invention preferably contains a curing accelerator. When using a curing accelerator, the amount used is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and usually about 0.5 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin.

Examples of the filler include silica, alumina, talc, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, silicon nitride, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, and silica alumina. Examples thereof include inorganic fillers such as fibers and silicon carbide fibers, and organic fillers such as polyester fibers, cellulose fibers, aramid fibers, and various polymer beads.
The thermosetting resin composition of the present invention may be used as it is without adding a filler, or may be used with a filler added. When the filler is added, the addition amount is not particularly limited as long as the effect of the present invention is exhibited, and the maximum is 95% by mass with respect to the total amount (mass) of the thermosetting resin composition containing the filler. Can be added.
Additives such as a silane coupling agent, a flame retardant, an oxidation stabilizer, a release agent, and a pigment other than the curing accelerator and the filler can be blended. These additives may not be added, but can be added as necessary. The amount of these additives used is not particularly limited as long as it does not impair the properties of the thermosetting resin composition of the present invention, and is in the range of 0 to 20% by mass in the thermosetting resin composition. Can be used.

  The ion scavenger is not particularly limited as long as it is capable of adsorbing and fixing impurity ions in the thermosetting resin composition, particularly various ions that reduce the reliability of the electronic circuit, Ion scavengers such as zirconium phosphate, titanium phosphate, antimony oxide, and bismuth oxide can be used. As these ion scavengers, DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.), Kyoward KW-2000 (manufactured by Kyowa Chemical Industry Co., Ltd.), IXE-100 (manufactured by Toagosei Co., Ltd.), IXE-300 (Toagosei Co., Ltd.) IXE-400 (manufactured by Toagosei Co., Ltd.), IXE-500 (manufactured by Toagosei Co., Ltd.), IXE-600 (manufactured by Toagosei Co., Ltd.) and the like are commercially available. These ion scavengers may be used alone or in combination of two or more. The usage-amount of an ion trapping agent is normally used in the range of 0-10 mass% in a thermosetting resin composition.

From the above, preferred thermosetting resin compositions of the present invention are as follows.
One of the preferred thermosetting resin compositions is
(I) The resin component (components (i), (ii) and (iii)) 85 to 100% by mass, preferably 90 to 100% by mass, and (II) resin components 0 to other than the resin component 0 to 15% by weight, preferably 0-10% by weight
And comprising at least one of the epoxy resin represented by formula (2) of the component (ii) and the epoxy resin curing agent represented by formula (5) of the component (iii) It is a resin composition.
In this case, the said resin component is more preferable than the following case.
Reactive polyamide resin (i): 40 to 95% by mass is preferable with respect to the total mass of the resin component (components (i), (ii) and (iii)), and 40 to 70% by mass is more preferable. Preferably, more preferably 40 to 65 mass%,
(ii) Epoxy resin: 15 to 50% by mass, more preferably 20 to 40% by mass, still more preferably 25 to 40% by mass, and most preferably 25 to 35% by mass, based on the total mass of the resin component. ,as well as
(iii) Epoxy resin curing agent: remainder, preferably 10 to 30% by mass, more preferably 15 to 30% by mass, still more preferably 15 to 25% by mass.

Examples of combinations of the preferred composition ratios of the above components (i), (ii) and (iii) include the following cases.
Reactive polyamide resin (i): 40 to 95% by mass relative to the total mass of the resin component,
(ii) Epoxy resin: 15 to 50% by mass, more preferably 20 to 40% by mass, still more preferably 25 to 40% by mass, and most preferably 25 to 35% by mass, based on the total mass of the resin component. ,as well as
(iii) epoxy resin curing agent: remainder,
Or
Reactive polyamide resin (i): 40 to 70% by mass relative to the total mass of the resin component,
(ii) Epoxy resin: 15 to 50% by mass, more preferably 20 to 40% by mass, still more preferably 25 to 40% by mass, and most preferably 25 to 35% by mass, based on the total mass of the resin component. ,as well as
(iii) epoxy resin curing agent: remainder,
It is.

In addition, the following cases may be mentioned as preferred combinations of the composition ratios of the other components (i), (ii) and (iii).
Reactive polyamide resin (i): 40 to 95% by mass is preferable with respect to the total mass of the resin component (components (i), (ii) and (iii)), and 40 to 70% by mass is more preferable. Preferably, more preferably 40 to 65 mass%,
(ii) epoxy resin: 15 to 50% by mass with respect to the total mass of the resin component, and
(iii) epoxy resin curing agent: remainder,
Or
Reactive polyamide resin (i): 40 to 95% by mass is preferable with respect to the total mass of the resin component (components (i), (ii) and (iii)), and 40 to 70% by mass is more preferable. Preferably, more preferably 40 to 65 mass%,
(ii) epoxy resin: 20 to 40% by mass with respect to the total mass of the resin component, and
(iii) epoxy resin curing agent: remainder,
It is.

  The thermosetting resin composition is more preferable when it further contains a curing accelerator. In this case, the content of the curing accelerator is about 0.5 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin. An imidazole compound is preferred as the curing accelerator.

The thermosetting resin composition of the present invention is usually used (or applied) in various electric / electronic materials as a resin solution dissolved or dispersed in a solvent, preferably a dissolved resin solution.
In the present invention, it is usually preferable to use the thermosetting resin composition of the present invention by forming it into a film as described below, for example.
The above-mentioned resin liquid (preferably resin solution) containing the thermosetting resin composition of the present invention is applied to a metal foil or a resin film (hereinafter referred to as a base film) and then dried to form a coating layer of the thermosetting resin composition As a base film having the above, it is used as it is, or a dry coating layer of a thermosetting resin composition is formed on a release film (a film subjected to a release treatment) in the same manner as described above, It can be used as it is, or it can be used as a thermosetting resin composition film by peeling the dry coating layer from the release film. In many cases, the resin liquid is used in a form that does not contain a filler. However, if necessary, the resin liquid may be blended and used. Further, as described later, a film-like substrate can be impregnated with the resin composition of the present invention and dried to be used as a prepreg or the like.
In the present invention, the film containing the thermosetting resin composition of the present invention includes any of the above-mentioned film molded products. In the case of the film molded product, it may contain a filler or may not contain a filler.

Application to the base film can be performed by a conventional method using a roll coater or a multi-coater. In addition, as the base film, electrical insulation such as metal foil such as copper foil or aluminum foil, polyimide film, aramid film, polyethylene terephthalate film, polyester film, polyetherimide film, polyether ketone film or polyphenylene sulfide film A resin film or the like is used.
The coating layer of the thermosetting resin composition is dried to such an extent that the curing reaction of the resin composition does not proceed or does not hinder the use of an adhesive or the like using a drying device such as an inline dryer. A layer comprising a thermosetting resin composition from which the solvent has been removed by performing the reaction at a temperature at which the curing reaction is suppressed, for example, about 120 to 140 ° C. for about 1 to 30 minutes, preferably about 1 to 15 minutes ( In the following, a film having simply a resin layer) can be obtained.
Moreover, the base film to be used is preferably subjected to a blasting treatment or a corona discharge treatment or the like in order to impart a mold release treatment or adhesion depending on the application.

The thermosetting resin composition can be directly used as an adhesive, but usually the film having the resin layer or the resin composition film obtained by peeling the resin layer described later from the release film as described above. And used as an adhesive.
A flexible wiring board, a laminate, an insulating material, or a protective material (for example, an insulating protective material) to which the resin composition of the present invention is applied can be obtained as follows.
For example, in the case of a film having a layer of a thermosetting resin composition on a base film that has been subjected to a release treatment, the film is removed after being pressure-bonded to an electronic substrate or the like, and if necessary, another film or a metal foil, etc. By laminating and curing by pressure and heating, a flexible wiring board, a laminated board, an insulating material, a protective material and the like using the resin layer as an adhesive or a protective film can be obtained.
In addition, the thermosetting resin composition film peeled off from the base film that has been subjected to the release treatment is applied to various electronic components, and is then molded using a molding machine such as a transfer mold, an injection mold, and the like. Various electronic components can be sealed and / or sealed by curing.
Further, a prepreg obtained by impregnating a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper with the resin solution, preferably the resin solution, and then drying by heating is subjected to hot press. A laminated board etc. can also be obtained by shape | molding and hardening | curing by.

The resin liquid containing the thermosetting resin composition of the present invention and the solvent used above can be obtained by dissolving or dispersing the thermosetting resin composition of the present invention in a solvent. Preferred is a resin solution in which the thermosetting resin composition of the present invention is dissolved. Examples of the solvent include solvents such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, xylene, acetone, methyl ethyl ketone or methyl isobutyl ketone. I can do it. These solvents may be used alone or in combination of two or more. Among these, a preferable solvent is dimethyl sulfoxide, and the resin solution dissolved in dimethyl sulfoxide is most preferable. The usage-amount of these solvents is the quantity which occupies normally 10-80 mass% with respect to the total mass of the thermosetting resin composition of this invention, and a solvent, Preferably it is 15-70 mass%.
The resin solution has a dry solid content of usually 20 to 90% by mass, preferably 20 to 70% by mass, more preferably 30 to 60% by mass, and still more preferably 30 to 50% by mass, with the balance being a solvent. Prepared as a resin solution. In some cases, it may be prepared as a resin solution having a solid content of 30 to 85% by mass and the balance being a solvent.
In the resin solution, the thermosetting resin composition of the present invention as a dry solid content contained in the solution may be any of the resin compositions described above, but preferably an epoxy represented by the formula (2) It is a thermosetting resin composition of the present invention containing at least one of a resin or an epoxy resin curing agent represented by formula (5), and more preferably, the following (a) or (b):
(A): a combination of the epoxy resin represented by formula (2) and at least one of the epoxy resin curing agents represented by formula (6) or formula (7), or (b): formula (5) ) And an epoxy resin curing agent represented by formula (3) or at least one of epoxy resins represented by (4),
It is the thermosetting resin composition of this invention containing any one combination of these.
As the content ratio of the epoxy resin and the epoxy curing agent in these resin compositions, the composition ratio of the epoxy resin and the epoxy curing agent can be applied as they are.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the physical-property value as described in an Example is calculated | required with the following method.
Active hydrogen equivalent of polyamide resin: The average mass number of a compound per hydrogen having a hydroxyl group and one hydrogen having an amino group, and is a theoretical value calculated from the charged amount of the raw material compound.
Epoxy equivalent: Average mass number of epoxy resin per epoxy group, measured according to JIS K-7236.
Hydroxyl equivalent: Average mass number of a compound per hydroxyl group (OH group), measured by an acetylation method according to JIS K-0070.
ICI viscosity: A value measured at 150 ° C. using an ICI viscometer (Cordix Co., Ltd.).
Glass transition temperature: Temperature at the maximum value of tan δ when a DMA measurement apparatus (RHEOLOGRAP-SOLID manufactured by Toyo Seiki Co., Ltd.) is used and measured at a heating rate of 2 ° C./min. (Note: DMA: Dynamic Mechanical Analysis: Dynamic Mechanical Analysis)
Adhesive strength: A value measured at 25 ° C. and 180 ° C. according to JIS C-6481 using a universal tensile testing machine (manufactured by Toyo Baldwin).
Elastic modulus lowering point temperature: The temperature at the intersection of the base line tangent before the dynamic elastic modulus decreases and the tangent of the line whose inclination becomes constant after the lowering in the dynamic elastic modulus curve in the DMA measurement.

Synthesis Example 1 (Synthesis of reactive polyamide resin)
650 parts by mass of N-methyl-2-pyrrolidone was charged into a 2 liter four-necked flask equipped with a thermometer, a condenser, a nitrogen inlet, and a stirrer, and 120 parts by mass of 3,4'-diaminodiphenyl ether while introducing nitrogen gas. Part, 96 parts by mass of isophthalic acid, 2.1 parts by mass of 5-hydroxyisophthalic acid, 6.3 parts by mass of lithium chloride, and 139 parts by mass of pyridine were stirred at 35 ° C. to dissolve them. Next, the liquid temperature was raised to 90 ° C., and 301 parts by mass of triphenyl phosphite was added dropwise in 2 hours, and the reaction was further performed for 5 hours. After completion of the reaction, 390 parts by mass of ion-exchanged water was added dropwise to the reaction solution over 2 hours, and the resulting solution was allowed to stand. After the liquid was separated into two layers, the upper layer was discarded. After adding 510 parts by mass of dimethyl sulfoxide (DMF) to the remaining lower layer slurry-like resin and dissolving at 60 ° C., the temperature was raised to 70 ° C. and 400 parts by mass of ion-exchanged water was added over 1 hour. After completion of the addition, the obtained liquid was cooled and allowed to stand. After the liquid was separated into two layers, the upper layer portion was discarded, and the remaining lower layer slurry-like resin was dissolved by adding DMF in an amount such that the resin concentration was 30% by mass to obtain a reactive hydroxyl group-containing polyamide resin solution. The theoretical value of active hydrogen equivalent of the obtained reactive hydroxyl group-containing polyamide resin is 5000 g / eq, and the values of n and m in the formula (1) are average values, n is about 50, and m is about 1. , M + n was about 51.

Synthesis Example 2 (Synthesis of epoxy resin represented by formula (3))
A 2 L 4-neck flask equipped with a thermometer, a condenser, and a stirrer is 173 parts by mass of XYLOCK 3L (Mitsui Chemicals, hydroxyl equivalent 173 g / eq) which is a phenol aralkyl compound (resin), 463 parts by mass of epichlorohydrin, 116 parts by mass of dimethyl sulfoxide (DMSO) was charged, and the resin was dissolved at 50 ° C. Then, 42 parts by mass of flaky sodium hydroxide (99% pure) was added to the obtained solution while introducing nitrogen gas with stirring over 2 hours. After completion of the addition, the mixture was reacted at 60 ° C. for 1 hour, 70 ° C. for 1 hour, and 80 ° C. for 30 minutes. After completion of the reaction, 300 parts by mass of water and 30 parts by mass of a 30% by mass aqueous solution of disodium hydrogen phosphate were added to the resulting reaction solution, followed by washing with water. The obtained liquid was allowed to stand, and after separation into two layers, the aqueous layer was discarded. Excess epichlorohydrin was distilled off from the remaining oil layer under heating and reduced pressure. Next, 600 parts by mass of methyl isobutyl ketone (MIBK) was added thereto to dissolve the oil layer residue. This methyl isobutyl ketone solution was heated to 70 ° C., 7 parts by mass of a 30% by mass aqueous sodium hydroxide solution was added with stirring, and then reacted for 1 hour. The obtained reaction solution was repeatedly washed with water, separated by liquid, and discarded of the aqueous layer until the pH of the aqueous layer after washing was neutral. Methyl isobutyl ketone was distilled off from the obtained resin solution under reduced pressure by heating to obtain 230 parts by mass (light yellow liquid) of the epoxy resin (A) represented by the formula (3). The epoxy equivalent of the obtained epoxy resin was 240 g / eq, and the ICI viscosity at 150 ° C. was 0.04 Pa · s. N in the formula (3) was 5.2 on average.

Synthesis Example 3 (Synthesis of epoxy resin curing agent represented by formula (5))
462.5 parts by mass of phenol was charged into a 2 L 4-neck flask equipped with a thermometer, a condenser, and a stirring device, and nitrogen gas was introduced to sufficiently purge the system. Next, 0.5 parts by mass of boron trifluoride phenol complex was added thereto, and then the temperature in the system was raised to 50 ° C. Next, 132.5 parts by mass of dicyclopentadiene was dropped therein over 1 hour while paying attention to heat generation, and the reaction was carried out. After completion of the dropping, the temperature in the system was raised to 70 ° C., and the reaction was further performed for 1 hour. After completion of the reaction, 300 parts by mass of methyl isobutyl ketone was added to the reaction solution, and 200 parts by mass of deionized water was further added, followed by washing with water. The mixed solution was allowed to stand, and after separation into an oil layer and an aqueous layer, the aqueous layer was discarded. Subsequently, excess phenol and methyl isobutyl ketone were distilled off from the remaining oil layer under heating and reduced pressure to obtain 301 parts by mass (light yellow transparent liquid) of the epoxy resin curing agent (E) represented by the formula (5). . The resulting epoxy resin curing agent had a hydroxyl group equivalent of 170 g / eq and an ICI viscosity at 150 ° C. of 0.05 Pa · s. The value of n in formula (5) was 1.8.

Examples 1-4, Comparative Example 1
Each component was mix | blended with the composition (mass part) shown in Table 1, and the thermosetting resin composition solution was obtained. Using a comma coater, apply these thermosetting resin compositions onto a release PET (polyester) film (PET-38AL5, manufactured by Lintec Corporation) so that the thickness after drying is 25 μm, and set at 130 ° C. The release PET film which has the layer of the thermosetting resin composition which is a hardened | cured material precursor was obtained by drying for 15 minutes with the floating drying furnace which was done. This thermosetting resin composition layer was peeled from the release PET film to prepare a thermosetting resin composition film. This film was cured in a drying oven under curing conditions of 160 ° C. × 4 hr + 200 ° C. × 6 hr to obtain a film-like cured product (cured product of thermosetting resin composition). Table 1 shows the glass transition temperature and elastic modulus lowering point temperature obtained from DMA measurement of the film-like cured product.
The thermosetting resin composition film is treated with a rough surface of electrolytic copper foil (CF-T9-18, manufactured by Fukuda Metal Foil Powder Co., Ltd.) and a polyimide film (Upilex 25-SGA, manufactured by Ube Industries, Ltd.). For adhesion test with flexibility that is adhesively compounded with a cured product of thermosetting resin composition film by sandwiching between surfaces and curing by heating at 180 ° C for 1 hour under pressure of 30 kg / cm 2 A sample was obtained. Table 1 shows the measurement results of the adhesive strength at the interface between the electrolytic copper foil and the film-like cured product of this adhesion test sample.

Each component described in Table 1 is as follows.
Polyamide resin solution: Reactive hydroxyl group-containing polyamide resin obtained from Synthesis Example 1 (active hydrogen equivalent 5000 g / eq) in a solid content of 30 wt% DMF solution Epoxy resin (A): Formula (3) obtained from Synthesis Example 2 An epoxy resin represented by (epoxy equivalent 240 g / eq)
Epoxy resin (B): Epoxy resin represented by formula (2) (Nippon Kayaku Co., Ltd., XD-1000, epoxy equivalent 245 g / eq)
Epoxy resin (C): epoxy resin represented by formula (4) (Nippon Kayaku Co., Ltd., NC-3000, epoxy equivalent 280 g / eq)
Epoxy resin curing agent (D): epoxy resin curing agent represented by formula (6) (Mitsui Chemicals, Zyloc-3L, hydroxyl group equivalent 173 g / eq)
Epoxy resin curing agent (E): epoxy resin curing agent represented by formula (5) obtained from Synthesis Example 3 (hydroxyl equivalent: 170 g / eq)
Epoxy resin curing agent (F): Epoxy curing agent represented by formula (7) (manufactured by Nippon Kayaku Co., Ltd., GPH-65, hydroxyl group equivalent: 173 g / eq)
Epoxy resin curing agent (G): Phenol novolac resin (Nippon Kayaku Co., Ltd., PN-80, hydroxyl equivalent 105 g / eq)
Curing accelerator: 2PHZ-PW (manufactured by Shikoku Kasei Co., Ltd.)
Solvent: DMF

The thermosetting resin composition of the present invention can be cured under a temperature condition of 200 ° C. or lower, which is lower than that of a general polyamide resin. The cured product has a low curing temperature from the results shown in Table 1. High heat resistance. Further, since the temperature at which the elastic modulus lowering point is high, the physical properties are stable in a wide temperature range from a low temperature to a high temperature, and particularly excellent adhesive properties at a high temperature.
Therefore, the thermosetting resin composition of the present invention and the cured product thereof are useful in a wide range of fields such as semiconductor devices, electronic devices, and automobile devices, in which thermal stress is expected in the manufacturing process and use environment.

Claims (18)

A reactive hydroxyl group-containing polyamide resin obtained by dehydration condensation reaction of 3,4'-diaminodiphenyl ether, isophthalic acid and 5-hydroxyisophthalic acid,
The following formula (2), formula (3) or formula (4)

(In the formula, n is an average value and represents a number exceeding 0 and 10 or less, and G represents a glycidyl group)
And at least one epoxy resin selected from the group consisting of compounds represented by formula (5), formula (6) or formula (7):

(In the formula, n is an average value and represents a number exceeding 0 and not exceeding 10)
A thermosetting resin composition comprising at least one epoxy resin curing agent selected from the group consisting of compounds represented by:   The content of at least one epoxy resin selected from the group consisting of the epoxy resins represented by formula (2), formula (3) and formula (4) is a reactive hydroxyl group-containing polyamide resin, an epoxy resin and an epoxy resin curing agent. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is 2 to 50% by mass with respect to the total mass of.   A film comprising the thermosetting resin composition according to claim 1.   A flexible wiring board to which the thermosetting resin composition according to claim 1 is applied.   A laminated board to which the thermosetting resin composition according to claim 1 is applied.   An insulating protective material to which the thermosetting resin composition according to claim 1 is applied.   An adhesive comprising the thermosetting resin composition according to claim 1.   A cured product of the thermosetting resin composition according to claim 1.   The thermosetting resin composition of Claim 1 containing at least any one of the epoxy resin represented by Formula (2) or the epoxy resin hardening | curing agent represented by Formula (5). (A) or (b) below
(A) a combination of the epoxy resin represented by formula (2) and at least one of the epoxy resin curing agents represented by formula (6) or formula (7), or (b) in formula (5) A combination of the epoxy resin curing agent represented and at least one of the epoxy resins represented by formula (3) or (4),
The thermosetting resin composition according to claim 9, comprising any one of the combinations.   The thermosetting resin composition according to claim 9, wherein both ends of the reactive hydroxyl group-containing polyamide resin are amino groups.   (i) a reactive hydroxyl group-containing polyamide resin, (ii) at least one epoxy resin selected from the group consisting of compounds represented by formula (2), formula (3) and formula (4), and (iii) formula (5) The total amount of at least one epoxy resin curing agent selected from the group consisting of compounds represented by formula (6) and formula (7) is based on the total amount of resin components in the thermosetting resin composition. The thermosetting resin composition according to claim 2 or 9, wherein the thermosetting resin composition is 85 to 100% by mass.   Furthermore, the thermosetting resin composition of Claim 2 or 9 containing a hardening accelerator.   The thermosetting resin composition according to claim 13, wherein the curing accelerator is an imidazole compound.   A thermosetting resin composition solution comprising the thermosetting resin composition according to claim 2 or 9 and a solvent.   The resin composition according to claim 15, wherein the solvent is dimethyl sulfoxide.   In the thermosetting resin composition, in at least one epoxy resin selected from the group consisting of epoxy resins represented by formula (2), formula (3) and formula (4), or in combination with other epoxy resins When it does, at least 1 type of epoxy resin hardening | curing agent chosen from the group which consists of a compound represented by Formula (5), Formula (6), and Formula (7) with respect to 1 equivalent of epoxy groups in the total amount of both, and reactivity When the average active hydrogen amount in the total amount of the hydroxyl group-containing polyamide resin or another epoxy resin curing agent is used in combination, the total amount of the epoxy resin curing agent including the other epoxy resin curing agent and the reactive hydroxyl group-containing polyamide resin The thermosetting resin composition according to claim 2 or 9, wherein the average amount of active hydrogen in the total amount of is 0.6 to 1.2 equivalents.   A flexible wiring board, a laminate or an insulating protective material to which the thermosetting resin composition according to claim 9 is applied, or an adhesive comprising the thermosetting resin composition according to claim 9.