WO2021177054A1 - 熱硬化性樹脂組成物及び繊維強化樹脂 - Google Patents

熱硬化性樹脂組成物及び繊維強化樹脂 Download PDF

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WO2021177054A1
WO2021177054A1 PCT/JP2021/006279 JP2021006279W WO2021177054A1 WO 2021177054 A1 WO2021177054 A1 WO 2021177054A1 JP 2021006279 W JP2021006279 W JP 2021006279W WO 2021177054 A1 WO2021177054 A1 WO 2021177054A1
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weight
compound
imide group
resin composition
thermosetting resin
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English (en)
French (fr)
Japanese (ja)
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竹己 松野
良隆 山田
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Nakata Coating Co Ltd
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Nakata Coating Co Ltd
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Priority to JP2021533820A priority Critical patent/JP7022868B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • thermosetting resin compositions and fiber reinforced resins relate to thermosetting resin compositions and fiber reinforced resins.
  • a thermosetting resin composition and a fiber reinforced resin (molded from these cured products) having an epoxy compound as a curing component and a predetermined polyimide compound as at least a cross-linking agent, having excellent heat resistance and being relatively inexpensive.
  • Including products The same shall apply hereinafter.
  • thermosetting resin composition containing an epoxy compound as a main component and a fiber reinforced resin using the same have considerable heat resistance (glass transition temperature Tg of about 200 ° C.). Further, such a thermosetting resin composition has advantages that it is excellent in adhesion to various reinforcing fibers and various resin substrates, and that it is relatively inexpensive and economically advantageous. .. Therefore, the thermosetting resin composition containing an epoxy compound as a main component has been widely used for prepregs further containing reinforcing fibers such as carbon fibers, and laminates for electric circuits using the prepregs (for example,). See Patent Document 1).
  • a polyimide molded product typified by a polyimide film is characterized in that it has more excellent heat resistance (about 300 ° C. at a glass transition temperature Tg) and electrical characteristics as compared with other resins. Therefore, a prepreg further containing a thermosetting resin composition containing a polyimide compound as a main component, a reinforcing fiber such as carbon fiber, or the like is compared with a thermosetting resin composition containing an epoxy compound as a main component. It is being studied for use as a heat-resistant material in a stricter environmental application, for example, in the aerospace field (see, for example, Patent Document 2).
  • thermosetting resin composition or the like containing the epoxy compound of Patent Document 1 as a main component does not have sufficient heat resistance (glass transition point is about 150 ° C. or less) of the obtained thermosetting product and is ultraviolet rays.
  • the weather resistance was poor due to the influence of the above. Therefore, at least in harsh environmental applications such as the aerospace field, there is a problem that it is practically difficult to use.
  • thermosetting resin composition containing the polyimide compound of Patent Document 2 as a main component has considerable heat resistance, it needs to be modified with a specific phthalic anhydride, and the cost is further increased. There was a problem that it became expensive and tended to be economically disadvantageous.
  • the inventors of the present invention have made heat resistant by using a predetermined polyimide compound at least as a cross-linking agent and using a predetermined amount, regardless of the type of epoxy compound, while using them as a curing component.
  • the present invention has been completed by finding that a thermosetting resin composition or the like having excellent properties and adhesion can be obtained at low cost. That is, the present invention provides a thermosetting resin composition having excellent heat resistance, adhesion, etc., low cost, and economically advantageous, and a fiber reinforced resin using such a thermosetting resin composition. The purpose is to provide.
  • thermosetting resin composition containing an epoxy compound as a curing component and at least an imide group-containing compound having a plurality of functional groups capable of reacting with an epoxy group as a cross-linking component that functions as a cross-linking component.
  • a thermosetting resin composition wherein the blending amount of the imide group-containing compound is in the range of 1 to 50,000 parts by weight with respect to 100 parts by weight of the epoxy compound. It is possible to solve the problems that have occurred.
  • thermosetting resin composition or the like having excellent adhesion and the like can be obtained at an extremely low cost.
  • the epoxy compound is an aqueous emulsion and the imide group-containing compound is an aqueous imide group-containing compound.
  • the epoxy compound itself as a curing component can be easily handled, and environmental safety can be enhanced. Further, it becomes easy to mix with an imide group-containing compound or the like as a liquid cross-linking component, and by extension, a thermosetting resin composition exhibiting more uniform characteristics can be obtained.
  • the epoxy compound is preferably a novolak epoxy compound.
  • the epoxy compound can be easily made water-based (including an emulsion; the same applies hereinafter).
  • it is a novolak epoxy resin (for example, orthocresol epoxy resin)
  • it is possible to easily mix it with a predetermined imide group-containing compound and obtain a thermosetting resin composition exhibiting more uniform characteristics. ..
  • the imide group-containing compound is an imide group-containing compound (partially hydrolyzed product) obtained by partially hydrolyzing a polyimide molded product. ..
  • the imide group-containing compound obtained by partially hydrolyzing the polyimide molded product also has self-crosslinking property at a low temperature (120 ° C. or lower), so that the obtained cured product has further heat resistance. It can improve the sex and weather resistance.
  • a so-called polyimide molded product can be recycled and used to obtain a partially hydrolyzed product. Therefore, the cost can be further reduced, and thus an economically advantageous thermosetting resin composition can be obtained.
  • the imide group-containing compound is preferably an aqueous imide group-containing compound.
  • the imide group-containing compound can be easily obtained by a method of dissolving a partially hydrolyzed product or the like in amine water, as described later.
  • thermosetting resin composition of the present invention at least one of an orthogic acid ester compound, a phytic acid compound, a dacro compound, and EDTA is contained as a viscosity stabilizer, and the amount of the viscosity stabilizer to be blended. Is preferably a value in the range of 0.01 to 20 parts by weight when the total amount of the epoxy compound and the imide group-containing compound is 100 parts by weight. With such a configuration, a predetermined viscosity stabilizer contributes and the storage stability of the thermosetting resin composition can be remarkably enhanced.
  • thermosetting resin composition of the present invention at least one particulate matter of carbon particles, inorganic particles and nanoparticles is further contained, and the blending amount of the particulate matter is contained in an epoxy compound and an imide group.
  • the value is preferably in the range of 1 to 300 parts by weight.
  • Another aspect of the present invention is a fiber containing an epoxy compound as a curing component, an imide group-containing compound having at least a plurality of functional groups capable of reacting with an epoxy group, and a reinforcing fiber, which functions as a cross-linking component.
  • the blending amount of the imide group-containing compound is set to a value in the range of 1 to 50,000 parts by weight with respect to 100 parts by weight of the epoxy compound as a curing component, and the blending amount of the reinforcing fiber is 1-10000 by weight. It is a fiber reinforced resin characterized by being worthy within the range of parts.
  • thermosetting resin composition contained as (in some cases, it may exhibit a function as a component), a fiber-reinforced resin or the like having excellent heat resistance, adhesion and the like can be obtained at low cost.
  • FIG. 1A illustrates the effect of the blending ratio of the epoxy compound as a curing component and the imide group-containing compound on the heat resistance evaluation (relative value of 10% weight loss temperature) based on the TG curve in TG-DTA.
  • FIG. 1B is a diagram provided for explaining the heat resistance (300 ° C., retention rate) of a cured product containing reinforcing fibers.
  • FIG. 2 is an FT-IR chart of an imide group-containing compound (Compound A in Table 1) obtained by partially hydrolyzing a polyimide molded product before curing.
  • FIG. 1A illustrates the effect of the blending ratio of the epoxy compound as a curing component and the imide group-containing compound on the heat resistance evaluation (relative value of 10% weight loss temperature) based on the TG curve in TG-DTA.
  • FIG. 1B is a diagram provided for explaining the heat resistance (300 ° C., retention rate) of a cured product containing reinforcing fibers.
  • FIG. 3 is an FT-IR chart of an imide group-containing compound (Compound A in Table 1) obtained by partially hydrolyzing a polyimide molded product after curing (150 ° C., 30-minute curing product).
  • FIG. 4 is a diagram for explaining the low temperature curability of an imide group-containing compound obtained by partially hydrolyzing a polyimide molded product.
  • FIG. 5 is a diagram provided for explaining a microphase separation phenomenon in a thermosetting resin composition (cured product).
  • FIG. 6 is a diagram (photograph) provided for explaining a curing method of a fiber reinforced resin (cured product) made of a thermosetting resin composition.
  • FIG. 7 (a) shows the appearance of a fiber-reinforced resin (250 ° C., 30-minute cured product) made of a thermosetting resin composition
  • FIG. 7 (b) shows the appearance of a fiber-reinforced resin made of a thermosetting resin composition. It is a figure (photograph) provided for explaining the appearance of a fiber reinforced resin (a product cured at 500 ° C. for 60 minutes), respectively.
  • FIG. 8A is an FT-IR chart of an imide group-containing compound (Compound B in Table 1) obtained by partially hydrolyzing a polyimide molded product
  • FIG. 8B is a polyimide.
  • 6 is an FT-IR chart of an imide group-containing compound (Compound C in Table 1) obtained by partially hydrolyzing a molded product before curing.
  • the first embodiment is a thermosetting resin composition containing an epoxy compound as a curing component and at least an imide group-containing compound having a plurality of functional groups capable of reacting with an epoxy group, which functions as a cross-linking component.
  • the thermosetting resin composition (including the cured product) is characterized in that the blending amount of the imide group-containing compound is in the range of 1 to 50,000 parts by weight with respect to 100 parts by weight of the epoxy compound. be.
  • the thermosetting resin composition of the first embodiment will be specifically described for each constituent requirement.
  • Epoxy compound (1) type The type of epoxy compound is not particularly limited, and is bisphenol type, diaminodiphenylmethane type, diaminodiphenylsulfone type, aminophenol type, metaxylene diamine type, 1,3-bisaminomethylcyclohexane type, At least one of isocyanurate type, hydantin type, phenol novolac type, orthocresol novolac type, trishydroxyphenylmethane type, tetraphenylol ethane type and the like can be used.
  • the epoxy compound is preferably a novolak epoxy compound (sometimes referred to as an orthocresol novolak type epoxy compound).
  • a novolak epoxy compound sometimes referred to as an orthocresol novolak type epoxy compound.
  • the epoxy compound is preferably an aqueous emulsion.
  • the epoxy compound itself which is a curing component, can be easily handled and the environmental safety can be enhanced. Further, it becomes easy to mix with an imide group-containing compound or the like as a liquid cross-linking component, and by extension, a thermosetting resin composition exhibiting more uniform characteristics can be obtained. Therefore, as described above, it can be said that the orthocresol novolac epoxy compound is particularly preferable among the epoxy compounds from the viewpoint of water solubilization.
  • the number average molecular weight of the epoxy compound is not particularly limited, but is usually preferably 400 g / mol or less. However, if the number average molecular weight is excessively small, the reactivity with the imide group-containing compound or the like may be significantly reduced. Therefore, the number average molecular weight of the epoxy compound is more preferably set to a value in the range of 30 to 350 g / mol or less, and further preferably set to a value in the range of 100 to 300 g / mol or less.
  • the epoxy equivalent of the epoxy compound is also not particularly limited, but is usually preferably set to a value of 300 g / eq or less. However, if the epoxy equivalent is excessively small, the reactivity with the imide group-containing compound or the like may be significantly reduced. Therefore, the epoxy equivalent is more preferably set to a value in the range of 50 to 200 g / eq, and even more preferably set to a value in the range of 100 to 150 g / eq.
  • the imide group-containing compound is characterized by having a plurality of functional groups capable of reacting with an epoxy group with respect to the type. That is, the imide group-containing compound has a plurality of carboxyl groups, amino groups, hydroxyl groups and the like, and at least functions as a cross-linking agent for the epoxy compound. Further, since the imide group-containing compound has such a plurality of functional groups, self-crosslinking at low temperature heating is also possible.
  • FIG. 1A excellent heat resistance can be exhibited in a predetermined thermosetting resin composition.
  • the horizontal axis of FIG. 1A shows the blending amount (parts by weight) of the predetermined imide group-containing compound with respect to 100 parts by weight of the epoxy compound in the thermosetting resin composition.
  • the vertical axis shows the relative value in the heat resistance evaluation (relative value of 10% weight loss temperature) based on the TG curve in TG-DTA. From the characteristic curve in FIG. 1 (a), it is understood that a considerable heat resistance evaluation can be obtained if the blending amount of the predetermined imide group-containing compound is 1 part by weight or more with respect to 100 parts by weight of the epoxy compound. It is understood that if the blending amount of the predetermined imide group-containing compound is in the range of 10 to 50,000 parts by weight, a considerable heat resistance evaluation can be obtained more stably.
  • thermosetting resin composition (cured product) containing the reinforcing fibers corresponding to Example 1 also has a retention rate in a thermogravimetric reduction test (up to 300 ° C. for 5 hours). Judging from the above, it is possible to show excellent heat resistance.
  • the horizontal axis of FIG. 1B shows the standing time (up to 5 hours) in the heating furnace every hour, and the retention rate (%) in the standing time in the cured product containing carbon fibers. Is taken and shown. From the change in mass reduction in FIG. 1 (b), the retention rate from the initial value was 95% by weight or more even when the cured product containing carbon fibers was left at a high temperature of 300 ° C. for 5 hours.
  • the retention rate of the cured product containing carbon fibers is based on the mass of the cured product containing carbon fibers measured using a chemical balance hj-II4200 (manufactured by Shinko Denshi Co., Ltd.).
  • the imide group-containing compound may be a predetermined imide group-containing compound (simply referred to as a partial hydrolyzate) obtained by partially hydrolyzing a polyimide molded product. ) Is preferable.
  • the reason for this is that if it is a partially hydrolyzed product, it also has self-crosslinking property at a low temperature (120 ° C. or lower), so that the obtained cured product can further improve heat resistance and weather resistance. That is, if it is a partially hydrolyzed product, it has a plurality of carboxyl groups, amino groups (including amide groups, the same applies hereinafter), hydroxyl groups, etc. as functional groups in one molecule, and is an epoxy. It can react with groups and can be self-crosslinked by low temperature heating.
  • FIG. 2 shows an example of an infrared spectroscopic spectrum chart of a partially hydrolyzed product before curing (measured by the ATR method), which has a predetermined structure having a carboxyl group, an amino group (amide group), a hydroxyl group, and the like. It is a polyimide compound (Compound A in Table 1).
  • FIG. 3 shows an example (measured by the ATR method) of an infrared spectroscopic spectrum chart of a partially hydrolyzed product (Compound A in Table 1) after thermosetting at 150 ° C. for 30 minutes. That is, from the comparison of FIGS. 2 and 3, it is understood that the peaks of the carboxyl group, the amino group (amide group) and the like are reduced, and the imide ring (peak A) is formed.
  • the partial hydrolyzate shown in FIG. 2 has an absorption peak (peak A) derived from an imide group at a wave number of 1375 cm -1 and an absorption peak (peak B) derived from an amide group at a wave number of 1600 cm -1.
  • the partially hydrolyzed product contains an imide group obtained by partially hydrolyzing a polyimide molded product of a predetermined size in the presence of water and a basic compound, for example, under a temperature condition of 50 to 100 ° C. It is preferably a compound. Then, such a partial hydrolyzate has at least an imide group, an amide group, a carboxyl group, a carbonyl group, and the like in the molecule composed of carbon atoms, so that the partial hydrolyzate is relatively as shown in FIG. It can be cured at low temperature (self-crosslinking) and reacted with the epoxy group of the epoxy compound. Further, such a partially hydrolyzed product is an imide group-containing compound that exhibits good solubility in various organic solvents and good adhesion to various equipment.
  • the horizontal axis shows the temperature at which the partial hydrolyzate is independently heated and cured, that is, the curing temperature (° C.), and the vertical axis shows the imide of the partial hydrolyzate.
  • the conversion rate is taken and shown. That is, from the Ft-IR chart, the imidization rate when heated at 250 ° C. for 30 minutes was set to 100%, and the peak height change of the imide group when heated at a heating temperature of 80 to 250 ° C. for 30 minutes was found to be imide. The conversion rate is calculated. Then, from the characteristic curve in FIG. 4, if the heating temperature is 100 ° C. and the heating is performed for about 30 minutes, an imidization rate of about 40% can be obtained, and if the heating temperature is 150 ° C. or higher, the heating is performed for about 30 minutes. It is understood that an imidization rate of almost 100% can be obtained.
  • thermosetting resin composition If it is a hydrolyzed imide group-containing compound, a so-called polyimide molded product can be recycled and used. Therefore, the production cost of the partially hydrolyzed product can be further reduced, and thus an economically more advantageous thermosetting resin composition can be obtained.
  • suitable polyimide molded products to be recycled for example, a polyimide film, a polyimide coating film, a polyimide resist, a polyimide electric component housing, a polyimide electronic component material, a polyimide container, a polyimide mechanical component, and a polyimide automobile.
  • the component include a circuit board in which a metal circuit pattern is formed on the surface of the polyimide film, a composite laminate such as TAB tape, and the like.
  • the average weight molecular weight of the imide group-containing compound is preferably set to a value in the range of 1000 to 100,000.
  • the reason for this is that by setting such an average weight molecular weight, a predetermined low-temperature curability can be obtained and good solubility in an organic solvent can be obtained. Therefore, the average weight molecular weight of the imide group-containing compound is more preferably set to a value in the range of 3000 to 60,000, and further preferably set to a value in the range of 5000 to 30000.
  • the average weight molecular weight of the imide group-containing compound is the same as that of other compounds, but can be measured as a polystyrene-equivalent molecular weight by gel permeation chromatography.
  • Blending amount The blending amount of the imide group-containing compound is set to a value within the range of 1 to 50,000 parts by weight with respect to 100 parts by weight of the epoxy compound. The reason for this is that if the blending amount of the imide group-containing compound is less than 1 part by weight, it becomes difficult to uniformly mix the compound, the cross-linking reaction becomes insufficient, or the microphase separation effect cannot be obtained. This is because it may occur. On the other hand, if the blending amount of the imide group-containing compound exceeds 50,000 parts by weight, it becomes difficult to adjust the heat resistance and fluidity of the thermosetting resin composition, and the mechanical properties and electricity of the obtained cured product are not only difficult to adjust. This is because it becomes difficult to adjust the characteristics, density, etc.
  • the blending amount of the imide group-containing compound is more preferably set to a value in the range of 5 to 10000 parts by weight, and set to a value in the range of 20 to 1000 parts by weight with respect to 100 parts by weight of the epoxy compound. Is more preferable, and it is more preferable that the value is in the range of 30 to 300 parts by weight.
  • the imide group-containing compound is a liquid, and more specifically, using an aqueous solvent containing water or alcohol as a solvent, the blending amount of the aqueous solvent is adjusted with respect to the total amount of the imide group-containing compound. Therefore, it is usually preferable to set the value in the range of 0.01 to 25% by weight. The reason for this is that if such an imide group-containing compound is in the state of an aqueous solution, not only is it easy to handle, but even an aqueous epoxy compound or the like can be blended in an accurate ratio, making it more uniform. This is because it can be a thermosetting resin composition.
  • the aqueous solvent (the concentration of the amine compound is such that a part or all of the amine compound is dissolved in advance in water, alcohol or the like as the aqueous solvent. , For example, 0.1 to 10% by weight) is also preferable.
  • examples of such an amine compound include an aromatic amine, a diamine compound, an aromatic diamine having two amino groups bonded to an aromatic ring and a hetero atom other than the nitrogen atom of the amino group.
  • 4-Oxazidin morpholine
  • pyrrolidine pyrrolidine and the like.
  • the blending amount thereof is set to a value within the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the imide group-containing compound contained in the imide group-containing compound in terms of solid content. It is preferable to do so.
  • thermosetting resin composition As the type of solvent (including dispersion) of the thermosetting resin composition, it is basically preferable to use water alone or water containing 0.1 to 30% by weight of an amine compound (amine-containing water). .. The reason for this is that if the solvent is such water, it can be easily and quickly scattered by heating at a temperature of at least 100 ° C. or higher, and further at 150 ° C. or higher after applying the thermosetting resin composition. This is because it can be effectively prevented from remaining in the surface treatment film. Further, if the water contains a predetermined amount of the amine compound, the imide group-containing compound can be easily dissolved to obtain an aqueous solution of the imide group-containing compound having a predetermined concentration.
  • thermosetting resin composition it is also preferable to add an organic solvent to water, or to use the organic solvent alone as a solvent without using water.
  • organic solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide, N, N-dimethylacetamide, methyl diglime, methyl triglime, dioxane, tetrahydrofuran, cyclohexanone, and cyclo.
  • At least one of pentanone, ⁇ -butyrolactone, toluene, ethyl acetate, butyl acetate, cellosolve, methyl ethyl ketone (MEK), anisole and the like can be mentioned.
  • Blending amount Regarding the blending amount of the solvent of the thermosetting resin composition is 40 to 99% by weight with respect to the total amount (100% by weight) of the thermosetting resin composition. It is preferable that the value is within the range. The reason for this is that the handling becomes easier by adjusting the blending amount of the solvent within a predetermined range. In addition, coating and drying becomes easier, and other compounding components such as thermoplastic resin components, thermosetting resin composition components, photocurable resin components, metal materials, ceramic materials, etc. can be uniformly and quickly applied. This is because it can be mixed.
  • the blending amount of the solvent is less than 40% by weight, the solubility of the imide group-containing compound and the mixing property with the epoxy compound become insufficient, and the handleability may be significantly lowered. Because there is.
  • the blending amount of the solvent exceeds 99% by weight, the viscosity is excessively lowered, it becomes difficult to form a uniform surface-treated film having a predetermined film thickness, and precipitates are likely to occur. This is because it may become. Therefore, the blending amount of the solvent is more preferably set to a value in the range of 50 to 90% by weight, and set to a value in the range of 60 to 80% by weight with respect to the total amount of the thermosetting resin composition. Is even more preferable.
  • Viscosity Stabilizer (1) Type it is preferable to add a predetermined viscosity stabilizer to the thermosetting resin composition. Therefore, it is preferable to add at least one of an orthoformate ester compound (trimethyl orthoformate, triethyl orthoformate, etc.), a phytic acid compound, a dacro compound, EDTA, and the like. That is, by blending a predetermined viscosity stabilizer, it is possible to capture and chelate metal ions that are thought to cause pseudo-crosslinking derived from a carboxyl group or a hydroxyl group, and suppress the increase in viscosity. Therefore, it has a low viscosity (100 to 100,000 mPsec, measurement temperature 20 ° C.) and can be easily filtered or easily applied.
  • an orthoformate ester compound trimethyl orthoformate, triethyl orthoformate, etc.
  • the blending amount of the predetermined viscosity stabilizer is preferably a value within the range of 0.01 to 10 parts by weight per 100 parts by weight of the imide group-containing compound (before the pseudo-crosslinked state).
  • the value is more preferably in the range of 0.1 to 7 parts by weight, and further preferably the value is in the range of 0.5 to 5 parts by weight.
  • thermosetting resin composition it is preferable to further contain at least one particulate matter (including fibrous matter) of carbon particles, inorganic particles and nanoparticles.
  • particulate matter including fibrous matter
  • the reason for this is that, for example, by including particulate matter having an average particle size (corresponding to a sphere) of 0.01 to 500 ⁇ m, not only the heat resistance and fluidity of the thermosetting resin composition can be easily adjusted. This is because the mechanical properties, electrical properties, density, etc. of the obtained cured product can be easily adjusted within a desired range.
  • Ceramic nanoparticles, nanopolyester fibers, nanocellulose fibers, nanopolyamide fibers and the like are preferably blended.
  • the blending amount of the particulate matter is preferably a value within the range of 1 to 100 parts by weight when the total amount of the epoxy compound and the imide group-containing compound is 100 parts by weight. The reason for this is that if the blending amount of the particulate matter is less than 1 part by weight, it becomes difficult to uniformly mix the particulate matter, and the blending effect may not be obtained. On the other hand, if the blending amount of the particulate matter exceeds 100 parts by weight, not only is it difficult to adjust the heat resistance and fluidity of the thermosetting resin composition, but also the mechanical and electrical properties of the obtained cured product. This is because it becomes difficult to adjust the density and the like within a desired range.
  • the amount of the particulate matter is more preferably set in the range of 5 to 80 parts by weight, and 10 to 50 parts by weight. It is more preferable that the value is within the range of the part.
  • thermosetting resin composition is usually set to a value within the range of 10 to 50,000 mPa ⁇ sec (measurement temperature: 25 ° C., solid content concentration: 20 to 60% by weight, the same applies hereinafter). Is preferable. The reason for this is that by limiting the viscosity to a predetermined range, not only is it easier to handle, but also good storage stability can be obtained. Further, the coatability is improved, and other compounding components such as a thermoplastic resin component, a thermosetting resin composition component, a photocurable resin component, a metal material, a ceramic material and the like can be uniformly and quickly compounded. Because. Therefore, the viscosity of the thermosetting resin composition is more preferably set to a value in the range of 100 to 10000 mPa ⁇ sec, and further preferably set to a value in the range of 300 to 5000 mPa ⁇ sec.
  • thermosetting resin composition an epoxy compound curing agent, an epoxy compound curing accelerator, an imide group-containing compound curing agent, an imide group-containing compound curing accelerator, an ultraviolet absorber, and an antiaging agent. It is preferable to add at least one additive such as a conductive material, an antioxidant, an infrared absorber, various elastomers, an adhesive strength improver, a dispersant, and a water repellent.
  • at least one additive such as a conductive material, an antioxidant, an infrared absorber, various elastomers, an adhesive strength improver, a dispersant, and a water repellent.
  • the value is usually preferably in the range of 0.01 to 30% by weight, preferably 0.1 to 10% by weight, based on the total amount (100% by weight) of the thermosetting resin composition. It is more preferable that the value is in the range of%.
  • thermosetting resin composition in order to improve the conductivity, antistatic property, etc. of the thermosetting resin composition, it is preferable to add a conductive material or an antistatic agent, but in that case, the thermosetting resin composition is usually used.
  • the value is preferably in the range of 0.5 to 30% by weight, more preferably in the range of 1 to 20% by weight, and 5 to 10 with respect to the total amount (100% by weight) of. It is more preferable that the value is in the range of% by weight.
  • a predetermined surfactant different from the above viscosity stabilizer is used. It is preferable to mix.
  • the blending amount of the predetermined surfactant is usually set to a value in the range of 0.005 to 10% by weight with respect to the total amount (100% by weight) of the thermosetting resin composition. Is preferable, the value is more preferably in the range of 0.01 to 8% by weight, and further preferably the value is in the range of 0.1 to 5% by weight.
  • the reason for this is that if the blending amount of the surfactant is less than 0.005% by weight, the addition effect may not be exhibited, and the blending amount of the surfactant exceeds 10% by weight. This is because the heat resistance and mechanical strength of the obtained polyimide resin film may decrease.
  • thermosetting resin composition of the present invention is not particularly limited, but for example, various resin films, resin molded products, metal films, metal molded products, ceramic films, raw materials for ceramic molded products, etc.
  • it can also be used as a thermosetting resin composition containing paper or wood. That is, although it depends on the mixing ratio of the epoxy resin contained in the thermosetting resin composition and the polyimide resin, even if the amount of the relatively inexpensive epoxy resin is large and the amount of the relatively expensive polyimide resin is small, it is predetermined. It is possible to obtain a thermosetting resin composition and a cured product thereof, which exhibit heat resistance and the like.
  • a reinforcing fiber, a film forming agent, or the like is blended, the length can be increased, and in that case, it is usually preferable to increase the length in a roll shape in the range of 10 m to 3000 m.
  • thermosetting resin composition of the first embodiment is a thermosetting resin composition for heat resistance, a thermosetting resin composition for ultraviolet resistance, a thermosetting resin composition for high dielectric constant, and an electric insulation resistance. It is suitable for at least one of a thermosetting resin composition, a thermosetting resin composition for a decorative material, and the like. Then, the thermosetting resin composition and the fiber-reinforced resin derived from the reinforcing fiber are heat-cured at a predetermined temperature to heat-resistant electric component housing, heat-resistant electric tape, heat-resistant light-reflecting tape, and heat-resistant. Molded electronic parts, heat-resistant circuit boards, heat-resistant containers, heat-resistant mechanical parts, heat-resistant automobile parts, UV-absorbing molded products, UV-absorbing films and the like can be preferably obtained.
  • a second embodiment is a fiber reinforced resin containing an epoxy compound as a curing component, an imide group-containing compound having a plurality of functional groups capable of reacting with an epoxy group, which functions as at least a cross-linking component, and reinforcing fibers. Therefore, the blending amount of the imide group-containing compound is set to a value in the range of 1 to 50,000 parts by weight with respect to 100 parts by weight of the epoxy compound, and the blending amount of the reinforcing fiber is set to 1-10000 parts by weight. It is a fiber reinforced resin (including a cured product).
  • the fiber-reinforced resin of the second embodiment will be specifically described for each constituent requirement.
  • Epoxy compound as a curing component can have the same contents as those described in the first embodiment, and thus the description thereof will be omitted again.
  • Imid group-containing compound At least the imide group-containing compound that functions as a cross-linking agent can have the same contents as those described in the first embodiment, and thus the description thereof will be omitted again.
  • reinforcing fiber (sometimes referred to as high-strength fiber, etc.) is not particularly limited, but is usually high-strength glass fiber, low-strength glass fiber, carbon fiber (carbon fiber). , Aramid fiber, aromatic polyester fiber, high-strength polyethylene fiber, and at least one of high-strength nylon fiber, nanofiber, cellac fiber and the like. Further, as such reinforcing fibers, it is also preferable to use two or more types of carbon fibers, glass fibers, aramid fibers, boron fibers, high-strength polyethylene fibers, alumina fibers, silicon carbide fibers and the like in combination. In the case of reinforcing fibers such as glass fiber and carbon fiber, any aspect such as twisted yarn, untwisted yarn and untwisted yarn can be used.
  • the adhesion to a predetermined thermosetting resin can be improved, and by extension, a cured product having more uniform mechanical properties, heat resistance, etc. can be obtained.
  • a coupling agent treatment, a siliceous flame treatment, a primer treatment, or the like to the surface of the reinforcing fiber. More specifically, it is preferable to form a surface treatment layer having a thickness of 1 nm to 3 mm by a predetermined surface treatment (including heat treatment in addition to the lamination treatment), and a surface treatment layer having a thickness of 10 nm to 1 mm is formed. It is more preferable to form a surface treatment layer having a thickness of 100 nm to 300 ⁇ m.
  • the reinforcing fibers are in the form of a sheet. That is, the form and arrangement of the fibers in the sheet-shaped reinforcing fibers are not limited, and for example, fiber structures such as long fibers aligned in one direction, a single tow, a woven fabric, a knit, and a braid are used. ..
  • thermosetting resin is uniformly and rapidly injected particularly through the non-woven fabric, and by extension, the mechanical properties, heat resistance, etc. are more uniform, and the large area (for example, a sheet-like material derived from a fiber-reinforced resin of 1 ⁇ 1 m 2 to 10 ⁇ 10 m 2 can be obtained.
  • the predetermined resin constituting the non-woven fabric includes polypropylene resin (including methyl polypropylene resin, crystalline polypropylene resin such as isotactic polypropylene and syndiotactic polypropylene, non-crystalline polypropylene resin, polyethylene resin mixed polypropylene resin, and the like).
  • polypropylene resin including methyl polypropylene resin, crystalline polypropylene resin such as isotactic polypropylene and syndiotactic polypropylene, non-crystalline polypropylene resin, polyethylene resin mixed polypropylene resin, and the like.
  • polypropylene resin including methyl polypropylene resin, crystalline polypropylene resin such as isotactic polypropylene and syndiotactic polypropylene, non-crystalline polypropylene resin, polyethylene resin mixed polypropylene resin, and the like.
  • the tensile elastic modulus measured in accordance with JIS R 7601 (2006) is preferably set to a value in the range of 200 to 440 GPa.
  • the tensile elastic modulus of the carbon fiber is affected by the crystallinity of the graphite structure constituting the carbon fiber, and the higher the crystallinity, the higher the elastic modulus. This range is preferable because all of the rigidity and strength of the carbon fiber reinforced composite material are balanced at a high level. Therefore, the tensile elastic modulus of the carbon fiber is more preferably a value in the range of 230 to 400 GPa, and further preferably a value in the range of 260 to 370 GPa.
  • the surface of the reinforcing fiber is subjected to a sizing treatment (including not only a polymer treatment but also a coupling treatment, a siliceous flame treatment and the like).
  • a sizing treatment including not only a polymer treatment but also a coupling treatment, a siliceous flame treatment and the like.
  • the fiber-reinforced resin (including a cured product) is characterized in that the blending amount of the reinforcing fiber is in the range of 1 to 1,000,000 parts by weight with respect to the epoxy compound as a curing component. ).
  • the reason for this is that if the blending amount of the reinforcing fibers is less than 1 part by weight, the blending effect of the reinforcing fibers does not occur, the mechanical strength of the cured product is insufficient, and the weight reduction effect is not exhibited. This is because it may be done.
  • the blending amount of the reinforcing fibers exceeds 1,000,000 parts by weight (1 million parts by weight), it becomes difficult to process the reinforcing fibers into a sheet or uniformly mix the epoxy compound / imide group-containing compound and the reinforcing fibers. This is because it may become. Therefore, although it depends on the application, it is more preferable that the blending amount of the reinforcing fiber is in the range of 10 to 10000 parts by weight, and in the range of 30 to 3000 parts by weight, with respect to the epoxy compound as a curing component. It is more preferable to set the value in the range of 50 to 500 parts by weight, and it is further preferable to set the value in the range of 50 to 500 parts by weight.
  • Example 1 Production of Thermosetting Resin Composition and Fiber Reinforced Resin (1) Step (1) A Kapton film as a polyimide molded product (mainly Kapton-100H, but a mixture of other Kapton films, manufactured by Toray DuPont Co., Ltd.) was cut into strips having a width of 10 mm or less using a chopper. Next, while adding dry ice and cooling, it is put into a resin crusher (model number P-1314, Horai Co., Ltd.) equipped with a punching metal having a diameter of 3 mm, and a polyimide molded product (average) that passes through the punching metal. Particle size (about 3 mm) was used as a polyimide pulverized product to be partially hydrolyzed.
  • a resin crusher model number P-1314, Horai Co., Ltd.
  • the granular imide group-containing compound contained about 0.2% by weight of potassium, about 0.02% by weight of Si, about 0.02% by weight of Ca, and 0.005% by weight of Fe, respectively. It was confirmed by quantitative analysis.
  • thermosetting resin composition was produced. That is, triethanolamine and water (20/100) were blended and uniformly mixed so that the solid content was 60% by weight to obtain an aqueous thermosetting resin composition. Then, in terms of solid content, the imide group-containing compound is based on 100 parts by weight of the aqueous emulsion epoxy compound (orthocresol novolac resin, manufactured by Japan Epoxy Resin Co., Ltd., product number: W1115 (Table 1, Type 1)). 30 parts by weight of (hydrolyzed imide group-containing compound / compound A) and a predetermined amount of water are mixed and stirred until uniform (solid content: about 30 weight). %) Was obtained.
  • the imide group-containing compound orthocresol novolac resin, manufactured by Japan Epoxy Resin Co., Ltd., product number: W1115 (Table 1, Type 1)
  • Step (4) The obtained prepreg was put into a predetermined mold 50 which is divided into two in the vertical direction as shown in FIG. 6 by sandwiching the obtained prepreg between two fluororesin films 52a and 52b in the vertical direction. That is, the prepreg is placed in the mold so that the start-up (L1) of the fiber-reinforced resin molded product is about 10 mm, the center width (L2) is about 50 mm, and the width of both wings (L3) is about 20 to 30 mm, respectively. It was charged and fixed by pressurization with the left and right pressing members 54.
  • the prepreg in the mold was heat-treated under the heating conditions of 250 ° C. for 30 minutes to prepare a fiber-reinforced resin molded product as shown in FIG. 7 (a).
  • the prepreg in the mold is heat-treated under the heating conditions of 500 ° C. and 60 minutes, the thermosetting resin composition is partially decomposed into a fiber-reinforced resin molded product as shown in FIG. 7 (b). I also confirmed.
  • thermosetting resin composition and fiber reinforced resin (including fiber reinforced resin molded product)
  • Stability of thermosetting resin composition (evaluation 1) The obtained thermosetting resin composition was allowed to stand at 25 ° C. for 3 months, and the storage stability was visually evaluated according to the following criteria. ⁇ : The color was transparent and no significant precipitate was observed. ⁇ : Partially turbid, but no significant precipitate was observed. ⁇ : Partially turbid, but a small amount of remarkable precipitate was observed. X: It becomes turbid and a remarkable precipitate is observed.
  • Adhesion (evaluation 3) The obtained prepreg was molded using a predetermined mold under heating conditions of 300 ° C. for 60 minutes. Next, a grid test was carried out in accordance with JIS K 5600, and the adhesion between the cured thermosetting resin composition and the reinforcing fibers was evaluated according to the following criteria.
  • ⁇ The number of residual grids is 100/100.
  • ⁇ The number of remaining grids is 95 or more / 100.
  • ⁇ The number of residual grids is 80 or more / 100.
  • X The number of residual grids is less than 80 / 100.
  • Example 2 the blending amount of the imide group-containing compound (partially hydrolyzed compound, compound A) is 50 parts by weight with respect to 100 parts by weight of the epoxy compound as a curing component in terms of solid content, and the epoxy compound.
  • the thermosetting resin composition and the fiber-reinforced resin were evaluated in the same manner as in Example 1 except that the carbon fibers were impregnated so that the compounding ratio was 10,000 parts by weight per 100 parts by weight.
  • Example 3 the blending amount of the imide group-containing compound (partial hydrolyzate, compound A) is 100 parts by weight with respect to 100 parts by weight of the epoxy compound in terms of solid content, and per 100 parts by weight of the epoxy compound.
  • the thermosetting resin composition and the fiber-reinforced resin were evaluated in the same manner as in Example 1 except that the carbon fibers were impregnated so that the compounding ratio was 50,000 parts by weight.
  • Example 4 the blending amount of the imide group-containing compound (partial hydrolyzate, compound A) was 150 parts by weight with respect to 100 parts by weight of the epoxy compound in terms of solid content, and the carbon fiber was treca (partially hydrolyzed, compound A). Same as in Example 1 except that carbon fiber is impregnated so that the compounding ratio is 10000 parts by weight per 100 parts by weight of the epoxy compound in addition to M-46J (manufactured by Toray Co., Ltd.). The thermosetting resin composition and the fiber-reinforced resin were evaluated.
  • Example 5 the amount of the imide group-containing compound (partial hydrolyzate, compound A) blended was 300 parts by weight with respect to 100 parts by weight of the epoxy compound in terms of solid content, and the carbon fiber was used as the epoxy compound.
  • the reinforced resin was evaluated.
  • Example 6 the polyimide molded product was changed to Kapton H (manufactured by Toray DuPont Co., Ltd.), the hydrolysis time thereof was changed to 36 hours, and the degree of hydrolysis of the polyimide molded product was changed to determine a predetermined value. It was designated as an imide group-containing compound (described as compound B in Table 1). Further, the thermosetting resin composition and the fiber reinforced resin were evaluated in the same manner as in Example 1, except that the solvent of the predetermined imide group-containing compound was NMP. In addition, FIG. 8A shows an FT-IR chart of a predetermined imide group-containing compound (compound B before curing).
  • Example 7 the type of epoxy compound as a curing component was 80 parts by weight of a commercially available orthocresol novolak resin (manufactured by Nagase ChemteX Corporation, product number: EM160, Table 1, Type 2) and bisphenol A type.
  • Epoxy resin (“Epiclon 1055” manufactured by Dainippon Ink and Chemicals Co., Ltd.) was made into a mixture of 20 parts by weight (Type 2 in Table 1).
  • the polyimide molded product was changed to Kapton EN (manufactured by Toray DuPont Co., Ltd.), the hydrolysis time was shortened to 12 hours, and the degree of hydrolysis of the polyimide molded product was changed.
  • the thermosetting resin composition and the fiber-reinforced resin were evaluated in the same manner as in Example 1.
  • FIG. 8B shows an FT-IR chart of a predetermined imide group-containing compound (compound C before curing).
  • Example 8 the types of the epoxy compound as the curing component were 70 parts by weight of a commercially available orthocresol novolac resin (manufactured by Yoshimura Oil Chemical Co., Ltd., product number: KE278) and a bisphenol A type epoxy resin (Dainippon Ink and Chemicals).
  • Example 1 and Example 1 except that 30 parts by weight of the mixture (Type 3 in Table 1) was prepared and the amount of the partially hydrolyzed product (Compound A) was 40 parts by weight.
  • the thermosetting resin composition and the fiber-reinforced resin were evaluated.
  • Comparative Example 1 In Comparative Example 1, instead of setting the blending amount of the predetermined imide group-containing compound to 0 parts by weight with respect to 100 parts by weight of the epoxy compound as a curing component, 10 parts by weight of paraphenyldiamine was blended as a diamino cross-linking agent. Except for the above, the thermosetting resin composition and the fiber-reinforced resin were evaluated in the same manner as in Example 1.
  • an epoxy resin as a curing component and an imide group having a specific structure as a cross-linking agent are contained.
  • the thermosetting resin composition obtained by blending the compound and the compound in a predetermined ratio not only has excellent heat resistance and adhesion, but also makes it possible to supply the thermosetting resin composition and the like.
  • thermosetting resin composition or the like which is considerably inexpensive and has excellent economic efficiency. Therefore, in the thermosetting resin composition of the present invention, the amount of the epoxy compound which is relatively inexpensive per unit weight is large, and conversely, the amount of the imide group-containing compound which is relatively expensive per unit weight is compounded. It can be said that the higher the amount, the lower the price of the obtained thermosetting resin composition.
  • the predetermined imide group-containing compound is a partially hydrolyzed product obtained by partially hydrolyzing a polyimide molded product as a so-called recycled product
  • the imide group-containing compound as a cross-linking component. It has become possible to further reduce the cost of.
  • a partially hydrolyzed product obtained by partially hydrolyzing a polyimide molded product also has self-crosslinking property at a low temperature (120 ° C. or lower), so that the obtained cured product has further heat resistance and weather resistance. It has become possible to improve the properties more than the polyimide alone product.

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4760105A (en) * 1985-10-09 1988-07-26 Westinghouse Electric Corp. Polyimide modified epoxy resins in aqueous emulsions for lamination and electrodeposition
JP2007091799A (ja) * 2005-09-27 2007-04-12 Kaneka Corp 熱硬化性樹脂組成物、及びその利用
JP2016199749A (ja) * 2015-04-10 2016-12-01 東洋紡株式会社 ポリイミド樹脂含有水性分散体組成物
JP2017014386A (ja) * 2015-07-01 2017-01-19 株式会社仲田コーティング ポリイミド樹脂組成物およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4760105A (en) * 1985-10-09 1988-07-26 Westinghouse Electric Corp. Polyimide modified epoxy resins in aqueous emulsions for lamination and electrodeposition
JP2007091799A (ja) * 2005-09-27 2007-04-12 Kaneka Corp 熱硬化性樹脂組成物、及びその利用
JP2016199749A (ja) * 2015-04-10 2016-12-01 東洋紡株式会社 ポリイミド樹脂含有水性分散体組成物
JP2017014386A (ja) * 2015-07-01 2017-01-19 株式会社仲田コーティング ポリイミド樹脂組成物およびその製造方法

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