JPS608247B2 - epoxy resin composition - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an epoxy resin composition that has excellent adhesive performance from low to high temperatures, and has excellent heat-resistant adhesive performance and water-resistant adhesive performance. In particular, it relates to an epoxy resin composition that exhibits excellent adhesion performance to metals. Demand for adhesives, especially adhesives for metals, is rapidly increasing in fields such as aircraft, automobiles, construction equipment, and machine assembly, but the performance of adhesives used in these technical fields is limited by low temperature. In addition to being excellent in adhesive performance such as tensile shear strength and T-peel strength under a wide range of temperature conditions from to high temperatures, it also has excellent adhesive performance such as water resistance and heat resistance durability, and excellent adhesion speed. High reliability is required for performance such as excellent workability. Conventionally, many types of adhesives have been known in terms of their composition. In particular, metal adhesives include acrylic adhesives, cyanoacrylic adhesives, epoxy adhesives, aliphatic polyamide adhesives such as nylon, aliphatic polyamide/epoxy adhesives, and vinyl/phenolic adhesives. , nitrile phenolic adhesives, polyimide adhesives, etc. have been widely used. Among these metal adhesives, acrylic adhesives, cyanoacrylic adhesives, epoxy adhesives, aliphatic polyamide adhesives such as nylon, and aliphatic polyamide/epoxy adhesives have high adhesive performance at high temperatures. Moreover, it has poor water-resistant adhesion performance and can only be used at temperatures below 100°C. In addition, although the adhesive performance of vinyl phenolic adhesives, nitrile phenolic adhesives, and polyimide adhesives has been improved considerably at high temperatures, it is still far from being sufficient, and they are inferior in terms of water-resistant adhesive performance. ing. None of the adhesives satisfies the performance required of post-adhesives for metals used in the above-mentioned technical fields, and they are only used for limited applications in limited fields. Conventionally, various polyamides have been proposed; for example, JomM1 of Polyamide
er Science, Part A, vo12, 181
~201 (19 mice) and JoumalofPoIMm
erScience, vol. 162, 33 ~ Spot (1962
), polyamides such as polysebacoylpiverazine and polyterephthaloyldimethylpiverazine have been proposed. In addition, Tsubaki Seki Publication No. 53-3323y discloses a hot-melt adhesive made of polysebacoylpiverazine with an average molecular weight of 10,000 and 50,000 and an epoxy resin with an average molecular weight of 300 and 2,000. Agent compositions have been proposed. However, since the epoxy resin composition proposed in the prior art document is of a hot-melt type, it has the advantage of being excellent in workability such as adhesion speed, but it has particularly high tensile shear strength and T-peel strength at high temperatures. It has the drawback of extremely low saddle adhesion performance, poor heat resistance and water resistance, and does not fully satisfy the adhesive properties required for post-adhesives for metals. The present inventors have demonstrated excellent adhesive performance such as tensile shear strength and T-peel strength under a wide range of temperature conditions from low to high temperatures, and excellent reliability in terms of performance such as heat resistance and water resistance. As a result of searching for an epoxy resin composition for adhesives with a high The epoxy resin composition of the present invention, which has been found to satisfy the above requirements and has arrived at the present invention, satisfies all the performances required of the metal adhesive, and is superior to, for example, the polyamide resin bush known as the prior art. Compared to conventional metal adhesives such as adhesives, epoxy resin adhesives, aliphatic polyamides, epoxy resin adhesives, and polysebacoylpiverazine/epoxy resin compositions, it has significantly superior adhesive performance at room temperature and heat resistance and durability. It's rusty. That is, the present invention provides (a' general formula [1] (wherein R1, R2, R3 and R4 are all hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, or 6 to 12 carbon atoms) represents an aryl group, n is 4 to 1
Indicates an integer of 0. This is an epoxy resin composition consisting of a polyamide containing as a main component an alkylene dicarbonylpiverazine component unit represented by the following: 'b} epoxy resin and {c} a curing agent for epoxy resin. The polyamide blended into the epoxy resin composition of the present invention has the general formula [1] (wherein R1, R2, R3 and R4 are all hydrogen atoms, 1 or 6 alkyl groups, or carbon atoms. represents a number 6 to 12 aryl group,
n represents an integer between 4 and 10. ) is a polyamide containing as a main component an alkylesodicarbonylpiverazine component unit. Here, the polyamide containing the alkylene dicarbonylpiverazine component unit represented by the general formula [1] as a main component is
In addition to the polyalkylene dicarbonyl piperazine composed only of alkylene dicarbonyl piperazine component units represented by the above general formula [1], alkylene dicarbonyl piperazine represented by the above general formula [1] as a constituent component It is a polyamide containing gin component units in a proportion of 50 mol% or more. The alkylene dicarbonylpiverazine component unit represented by the general formula [1], which is a constituent component of the polyamide blended in the epoxy resin composition of the present invention, is represented by the general formula

[0] (wherein R1, R2, R3 and R4 all represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms) When it is a lupiberazine component unit, it is preferable because the adhesive performance and heat resistance durability at room temperature of the resulting epoxy resin composite are improved. In the polyamide blended into the epoxy resin composition of the present invention, minor components contained in addition to the alkylene dicarbonylpiverazine component unit represented by the general formula [1] are usually represented by the general formula [1].
m] (wherein R1, R2, R3 and R4 all represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R5 has 11 to 12 carbon atoms. , a 20 alkylene group or an arylene group having 6 to 12 carbon atoms) or a free range carbonylpiverazine unit. The component unit represented by the general formula [m], which is a small amount of the constituent component of the polyamide blended in the epoxy resin composition of the present invention, is represented by the general formula [W] (where R1, R2, R3 and R
Each of 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and X represents a hydrogen atom or a carboxyl group. ) is particularly preferable because it improves the adhesive performance of the resulting epoxy resin composition, such as high temperature adhesive performance, heat resistance durability, and water resistance durability. Specifically, the carboxyphthaloylpiverazine component unit represented by the general formula [W] is represented by the general formula [Wa] to [Wd], (in the formula,
R1, R2, R3 and R4 all represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ) is a carboxyphthaloylpiverazine component unit. The polyamide blended into the epoxy resin composition of the present invention includes the alkylene dicarbonyl biverazine component unit represented by the above general formula [1] and the above general formula [W]
In the case of a polyamide consisting of carboxyphthaloylpiverazine component units represented by the above general formula [1], the composition thereof is usually 50% to 97% by mole, The amount of carboxyphthaloylpiverazine component units represented by the general formula [W] is preferably in the range of 65 to 95 mol%, and usually in the range of 3 to 50 mol%, preferably 5 to 35 mol%. General formula [1] and general formula [1] constituting the polyamide blended in the epoxy resin composition of the present invention
B], general formula [m], general formula [W], general formula [Wa],
General formula [Wb], general formula [Wc] and general formula [Wd]
In the structural units, R1, R2, R3 and R4 each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a bentyl group, a hexyl group, a phenyl group, a tolyl group, a naphthyl group, etc. be able to. Moreover, in the structural unit of the general formula [1],
Specific examples of the alkylene group represented by xC02n include a tetramethylene group, a bentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group. In addition, in the structural unit of the general formula [m], R5 is an undecamethylene group, a dodecamethylene group, a phenylene group, a 2-carboxy-1,4-phenylene group, a 4-carboxy-1,3-phenylene group, a 2,5-dicarboxy- 1
, 4-phenylene group, 4,6-dicarboxy 1,3-
Examples include phenylene group and naphthylene group. Furthermore, the general formula [1], general formula [n], general formula [m] general formula [W], general formula [Wa], general formula [Wb]
, specifically as the piperazine component units in the constituent components of the general formula [Wc] and the general formula [Wd], piperazine,
2-methylpiverazine, 2-ethylpiverazine, 2-propylpiverazine, 2-inpropylpiverazine, 2-
butylpiverazine, 2-bentylphiverazine, 2-phenylpiverazine, 2-tolylpiverazine, 2,5-dimethylpiverazine, 2,5-diethylpiverazine, 2,5
-diisopropylpiverazine, 2,5-diphenylpiverazine, 2,3,5,6-tetramethylpiverazine, 2
, 3,5,6-tetraethylpiverazine and the like. Among these piperazine component units, piperazine, 2-methylpiverazine, 2,6-dimethylpiverazine, 2-ethylpiverazine or 2,5-jethylpiverazine are preferably used. In addition, the dicarpone brewing component units represented by the general formula [1] among the constituent components of the polyamide include adipic acid, pimelicic acid, suberic acid, azelaic acid, sebacic acid, nonamethylene dicarboxylic acid, and decamethylene dicarboxylic acid, which are the main components. In addition to the acid, undecamethylene dicarboxylic acid, dodecamethylene dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, as minor components and dicarboxylic acid component units included in the above general formula [m] Examples include acids. Moreover, examples of the polycarposo brewing component unit included in the general formula [m] include trimellitic acid and pyromellitic acid. The polyamide can be produced by conventional methods. For example, polyalkylene dicarbonyl piperazine consisting only of alkylene dicarbonyl piperazine component units represented by the general formula [1] is produced from the above-mentioned piperazine and alkanedicarboxylic acid dihalide by a conventional solution polymerization method or interfacial polymerization method. can do. Further, the polyamide containing the carboxyphthaloylpiverazine component unit represented by the general formula [N] as a minor component is a mixture consisting of a piperazine, an alkanedicarboxylic acid dihalide, and the trimellitic anhydride halide and/or pyromellitic anhydride. It can be produced by interfacial polymerization method or solution polymerization method. The weight of the polyamide blended into the epoxy resin composition of the present invention is usually in the range of 0.2 to 3.0, preferably 0.4 to 2.5. The epoxy resin 'b' blended into the epoxy resin composition of the present invention is a compound having two or more epoxy groups in one molecule. Specifically, such epoxy resins include, for example,
Bisphenol A, bisphenol F, 1, 1, 2, 2
- Glycidyl ether type epoxy resin of polyphenol compounds such as tetrakis(4-hydroxyphenyl)ethane: Glycidyl ether type epoxy resin of nuclear hydride of the polyphenol compound; Power 7 Call, resorcin, hydroquinone, phloroglucin Glycidyl ether type epoxy resin of polyhydric phenols such as ethylene glycol, butanediol, glycerol, erythritol, polyoxyalkylene glycol; Nopolac type epoxy resin; Alicyclic epoxy resins such as vinyl cyclohexene dioxide, limonene dioxide, and dicyclobentadiene oxide; polyglycidyl ester epoxies made from ester condensates of polycarboxylic acids such as phthalic acid and cyclohexane-1,2-dicarboxylic acid. resin:
Examples include polyglycidylamine-based epoxy resin; methylepoxy resin. Among these epoxy resins, it is preferable to use a glycidyl ether type epoxy resin of polyphenol compounds or a novolak type epoxy resin, and it is particularly preferable to use a glycidyl ether type epoxy resin of bisphenol A or bisphenol F. As the curing agent (c) for epoxy resins to be blended into the epoxy resin composition of the present invention, any compound generally known as a curing agent for epoxy resins can be used. For example, specifically, chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenebentamine, dibropylene diamine, and diethylaminopropylamine; cycloaliphatic polyamines; aliphatic polyamine adducts; ketoimines; modified aliphatic polyamine; polyamide amine; aromatic amine; aromatic modified amine; aromatic modified polyamine; tertiary amine curing agent; mercaptan curing agent; acid anhydride curing agent; ethylene-maleic anhydride copolymer Copolymers having acid anhydride groups such as polymers; compounds having phenolic hydroxyl groups such as novolac type or resol type phenol resin initial condensates; compounds such as dicyandiamide; and melamine. In particular, in order to keep the epoxy resin composition stable for a long period of time, the curing agent added to the epoxy resin composition used as a twilling agent does not act at room temperature but decomposes at high temperature to release at least one kind of active hydrogen. Those containing at least one nitrogen-containing compound that yields amine-containing compounds are preferred. Examples of such curing agents include dicyandiamide, dicyandihydrazide, alkylamine/borane chloride, BF3/amine rust, imidazoles, etc., and curing agents containing both dicyandiamide and substituted urea are particularly preferred. . The epoxy resin composition of the present invention can also be used as a composition consisting only of the above three components. In addition to the above three components, metal powders such as iron, stainless steel, and aluminum, inorganic oxides such as titanium dioxide, aluminum oxide, silicon oxide, and calcium oxide, metal chromates, zinc, cadmium, strontium, lead, and barium may be added as necessary. Fillers such as corrosion-resistant pigments, stabilizers, etc. can also be blended. The blending ratio of each component of the epoxy resin composition of the present invention is as follows. The blending ratio of the polyamide 'a- is the same as that of the epoxy resin (
b) Usually in the range from 15 to 80 parts by weight, preferably from 20 to 70 parts by weight, per 100 parts by weight.
Further, the blending ratio of the curing agent tc for the epoxy resin is usually 0.5 parts by weight per 100 parts by weight of the epoxy resin (b).
None, 100 parts by weight, preferably 0.5 None, 50 parts by weight
Parts by weight range. Furthermore, the above-mentioned fillers and extenders, which are blended as necessary in the epoxy resin composition of the present invention,
Stabilizers and the like are used in appropriate amounts. The epoxy resin composition of the present invention has excellent adhesive properties such as tensile shear strength and T-peel strength under a wide range of temperature conditions from low to high temperatures when used as an adhesive, particularly as an adhesive for metals, and has excellent heat resistance. It is characterized by excellent performance such as durability and water resistance, and is compatible with conventional polyamide adhesives, epoxy resin adhesives, aliphatic polyamide/epoxy resin adhesives, and polysebacoylpiverazine/epoxy resins. It has significantly superior adhesive performance at high temperatures and water-resistant adhesive performance compared to metal adhesives such as compositions. The epoxy resin composition of the present invention can be used to bond adherends such as metal, wood, plastics, fibers, stone, porcelain, and glass. Among these adhesives, the epoxy resin adhesive of the present invention is particularly excellent as an adhesive for metals, such as adhesion between metals or adhesion between metals and other adhesives. Adherent metals include iron, aluminum, copper, chromium,
Examples include nickel, titanium, zirconium, tin, zinc, gold, silver, and various alloys containing the above metal components. When the epoxy resin composition of the present invention is used to bond metal among the adherends, it is preferable to subject the metal to a surface treatment. As the surface treatment method, various methods are employed depending on the purpose, such as mechanical polishing, chemical treatment, and surface cleaning with a solvent such as trichloroethylene or acetone. Next, the epoxy resin composition of the present invention will be specifically explained using Examples. [1] Reference example for producing polyamide 1 Piverazine 5.16 g (6 hM), triethylamine 12.1 hM (120 hM) and methylene chloride 10 hM
The mixture was placed in a four-necked flask equipped with a thermometer, a reflux condenser, and brought to room temperature under an N2 atmosphere. 10 hours) solution was added dropwise for 1 minute, then 30 hours
The reaction was carried out for 1 hour. The reaction mixture was diluted with hexane, and the precipitated polymer was collected by passing it through a suction furnace using a glass filter filter. After dispersing the polymer in 1 volume of water and pulverizing it using a mixer, the polymer was washed with water and heated for 10 minutes in an open vacuum.
11. Dry for 1 day under low ship Hg condition. Foundation (75%)
of polysebacoylpiverazine was obtained. polymer
(cone.QS04, 30q○) is 1.2 evening/g
Met. Reference Example 2 Polysebacoyl-
2,5-dimethylpiverazine was synthesized. The yield (yield) of the polymer is 12. Female (71.3%), [
] is 0.84 dso/g (conc. day 2 S04, 3
0q○). Reference Examples 3 to 5 In Reference Example 2, instead of using sebacoyl chloride, Table 1
A polyamide was synthesized in the same manner as in Reference Example 2, except that the dicarboxylic acid dichlorides shown in Table 1 were used. The results are shown in Table 1. Table 1 (Note 1) conc, day 2S04 at 30°C (Note 2) The adipoyl-2,5-dimethylpiverazine component unit in the polymer was 45 moles. Reference example 6 In reference example 1, sebacoyl chloride 14.3
Sebacoyl chloride 12.91 instead of using Tsuru (60hM)
g (54mM), terephthaloyl chloride 1.2 crabs (ahM
) was used, but in the same manner as in Reference Example 1, a copolyamide consisting of sebacoylpiverazine and terephthaloylpiverazine component units was synthesized. The yield of polymer is 12. Acid (83.1%), [ri](c
omc. QS04 (30°C) is 1.0/g, and the sebacoyl piverazine component unit in the copolymer is 91 mol%.
Met. Reference example 7 Piverazine 6.8 thighs (8 hM)
, 16 MM of triethylamine, and 250 mL of methylene chloride were placed in a four-necked flask equipped with a thermometer and a reflux condenser, and the mixture was heated at room temperature under an N2 atmosphere. Sebacoil 14. A solution of 1 g of milk (6 M) in methylene chloride (100 M) was added dropwise over 1 minute, followed by a 3-part reaction at 3° C. To this reaction mixture was added 4.21 g of trimellitic anhydride chloride.
A methylene chloride (100%) solution of g (2 hM) was added dropwise over 1 minute, and the reaction was carried out at 40°C for 1 hour. The post-treatment of the reaction was carried out in the same manner as in Reference Example 1, and a copolyamide consisting of sebacoylpiverazine and carboxyphthaloylpiverazine component units represented by the general formulas [Wa] and [Wb] was A female (92.0%) yield was obtained. Copolymerized polyamide (com.
4, 30° C.) was 0.94 d, and the sebacoylpiverazine component unit in the copolyamide was 79 mol%. Reference example 8 In reference example 7, sebacoyl chloride 14.3 (skin hM)
and 4.21 g of trimethic anhydride chloride (2 hM
) instead of using 1626 g of sebacoyl chloride (Makkite M) and 2.5 cycles of trimellitic anhydride chloride (12 hM)
A copolymerized polyamide was obtained in a yield of 184 pieces (9 u %) by the method described in Reference Example 7 except for the above. Copolymerized polyamide (comH2S04 "30")
qo) was 1.02 dso/g, and the sebacoylpiverazine component unit in the copolyamide was 88 mol%. Reference Example 9 The method described in Reference Example 8 was used except that 2.6 g of pyromellitic anhydride (12 hM) was used instead of trimellitic anhydride chloride in Reference Example 8, and pyromellitic anhydride was added in the form of powder. Sebacoylpiverazine, a copolyamide consisting of dicarboxyphthaloylpiverazine component units represented by the general formula [Nc] and the general formula [Wd], i8
．． A yield of 4 females (% total) was obtained. The 〔ri〕 of Kyodoaipo lj amide is 0. non-genyu/g(con
c. During H-exchange 04 (30°C), the sebacoylpiverazine component unit was 90%. [0] Preparation of Epoxy Resin Composition A 10% methylene chloride solution of the polyamide described in the reference example was prepared, and a predetermined amount of bisphenol A-based epoxy resin ("Epomic R-140" manufactured by Mitsui Petrochemical Epoxy Co., Ltd.) was added to this.
or R-144, epoxy equivalent is 190, 25 respectively
5) and a predetermined amount of cycyandiamide were added and allowed to stand at room temperature for one day to prepare an epoxy resin composition. An adhesive test piece was prepared using this solution. [m] Preparation of post-attached test piece The epoxy resin composition was 10 m in length, IQ in width and 1 in thickness.
The solution was applied to the tip (1) of a stainless steel plate (SUS304, finished, acetone degreased) and dried at room temperature for 2 hours and then at 40°C for 3 minutes (solid content thickness approximately 50°C). After that, put the coated surfaces together, and under the pressure of 200 pm 01k9/ground 1
A tensile shear test piece was prepared by pressing and bonding for a while. Also T
The mold peeling test piece was made by applying an epoxy resin composition to the tip (3 mosquitoes x 25 pigs) of a stainless steel plate (SUS304, finished, acetone degreased) with a length of 180 mm, width of 25 mm, and thickness of 300 mm. The subsequent operations were performed under the same conditions as for the tensile shear test piece. Example 1 Reference Example 1 100 parts by weight of the polyamide described above, epoxy resin (manufactured by Mitsui Petrochemical Epoxy Co., Ltd. ~ trade name: Meiko Pomic R)
-144) An adhesive test piece was prepared using an epoxy resin composition consisting of 10 parts by weight of dicyandiamide and 82 parts by weight of dicyandiamide. The protruding portion was scraped off, held in an air atmosphere at a predetermined temperature for 10 minutes, and the strength at the predetermined temperature was measured by tensile shearing the test piece at a tensile rate of 50 skins/min. 3 tensile shear test pieces
The specimens were kept at 200 oo in an air atmosphere for 0 days, and the tensile shear strength at 24 oo was measured to determine their heat aging resistance.Furthermore, the tensile shear test was conducted by immersing them in boiling tap water of 97 to 100 qo for 1 day, and then taking them out. The tensile shear strength was measured after holding at 24℃ for 10 minutes, and it was determined that the T-type peel strength was 24℃. It was measured by peeling it off into a mold.The results are shown in Table 2.Example
12-14 Epoxy resin compositions were prepared using the polyamides, epoxy resins, and dicyandiamides shown in Table 2 at the mixing ratios shown in Table 2, and adhesive test plates thereof were prepared. Adhesive strength was measured by the method described in Example 1. Table 2 shows the results.
It was shown to. Comparative Example 1 An epoxy resin composition and an adhesive test piece were prepared in the same manner as in Example 1 except that dicyandiamide was not used. The results are shown in Table 2. Comparative Example 2 In Example 1, instead of using polysebacoylpiverazine, aliphatic copolymerized nylon (Amiran CM400 manufactured by Toray K.K.) was used. Also, instead of using methylene chloride for preparing the epoxy resin composition, triclene was used. An epoxy resin composition and an adhesion test piece were prepared in the same manner as in Example 1, except that a mixture of equal weights of 1/3 was used. The results are shown in Table 2. Comparative Example 3 An epoxy resin composition and an adhesive test piece were prepared by the method described in Example 1 using polysebacoylpiverazine and methylene chloride. The results are shown in Table 2. Comparative Example 4 Using a film-like nitrile phenolic adhesive (manufactured by Sony Chemical KK, product name ○-1 3032), 5
An adhesion test piece was prepared by crimping between two females at a pressure of k9/base and 20,000 yen. The results are shown in Table 2. Comparative Example 5 Epoxy adhesive (manufactured by Cemedine K.K., trade name EP-
106), this was applied to a stainless steel plate, overlapped, and cured for 20 minutes at 150°C under a pressure of 0.5k9/ground to prepare an adhesive test piece. The adhesion test was conducted in the same manner as in Example 1. The results are shown in Table 2. Comparative Example 6 Using a modified acrylic adhesive (manufactured by Denki Kagaku K.K., trade name: Hardlock C-320), a test piece was prepared by curing at room temperature for 7 days under a pressure of 0.5 k9/s. The adhesion test was conducted in the same manner as in Example 1. The results are shown in Table 2. Table 2

Claims (1)

[Claims] 1 (a) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2, R^3 and R^4 are all hydrogen atoms or represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and n
represents an integer from 4 to 10. An epoxy resin composition comprising a polyamide containing as a main component an alkylene dicarbonyl piperazine component unit represented by (b) an epoxy resin, and (c) a curing agent for epoxy resin. 2 The blending ratio of the polyamide (a) is higher than that of the epoxy resin (
b) The epoxy resin composition according to claim 1, in the range of 15 to 800 parts by weight per 100 parts by weight. 3 The blending ratio of the curing agent (c) for epoxy resin is 0.5 to 10 parts by weight per 100 parts by weight of the epoxy resin (b).
Claim 1 or 2 in the range of 0 parts by weight
The epoxy resin composition described in . 4 Polyamide (a) or general formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1, R^2, R^3 and R^4 are all hydrogen atoms, number of carbon atoms is 1 6 to 6 alkyl group or C6 to 12 aryl group. Any epoxy resin composition.
5 Polyamide (a) has the general formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1, R^2, R^3 and R^4 are all hydrogen atoms, the number of carbon atoms represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and n is 4
Indicates an integer from 1 to 10. ) and a range of 50 to 97 mol% of alkylene dicarbonyl piperazine component units represented by formula [IV]
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2, R^3 and R^4 are all hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, or 6 to 6 carbon atoms. 12 aryl groups, and X represents a hydrogen atom or a carboxyl group. Any of the epoxy resin compositions described in section. 6 Polyamide (a) has the general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2, R^3 and R^4 are the same as above.) The sebacoylpiperazine component unit represented is in the range of 50 to 97 mol% and the general formula [IV] ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1, R^2, R^3 and R^4 and Resin composition. 7 The carboxyphthaloylpiperazine component unit represented by the general formula [IV] constituting the polyamide (a) is represented by the general formula [IVa] or the general formula [IV].
IVd] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1, R^2, R^3 and R^4 are the same as above.) At least one carboxyphthaloylpiperazine The epoxy resin composition according to claim 5 or 6, which is a component unit.