JP7022868B2 - Thermosetting resin composition and fiber reinforced plastic - Google Patents

Description

The present invention relates to a thermosetting resin composition and a fiber reinforced resin.
In particular, 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.)

Conventionally, a 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, the thermosetting resin composition has the advantages of being excellent in adhesion to various reinforcing fibers and various resin base materials, and being 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 laminated boards for electric circuits using the prepregs (for example,). See Patent Document 1).

On the other hand, a polyimide molded product typified by a polyimide film is characterized by having further 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).

JP-A-2007-262198 (Claims, etc.) Japanese Patent Application Laid-Open No. 2006-312700 (Claims, etc.)

However, the thermosetting resin composition or the like containing the epoxy compound of Patent Document 1 as a main component has insufficient heat resistance (glass transition point of about 150 ° C. or less) of the obtained thermosetting product and is ultraviolet rays. There was a problem that the weather resistance was poor due to the influence of such factors.
Therefore, at least in harsh environmental applications such as the aerospace field, there is a problem that it is practically difficult to use.

Further, although the 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 specific phthalic anhydride, and the cost is further increased. There was a problem that it became expensive and tended to be economically disadvantageous.

Therefore, as a result of diligent studies, 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.

According to the present invention, 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 as a cross-linking component that functions as a cross-linking component. A thermosetting resin composition is provided, which comprises a thermosetting resin composition in which 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.
That is, while the epoxy compound is used as a curing component, by using at least a predetermined amount of the polyimide compound as a cross-linking agent (some may self-crosslink and exhibit a function as a curing component), heat resistance and heat resistance can be obtained. A thermosetting resin composition or the like having excellent adhesion and the like can be obtained at an extremely low cost.

Further, in constructing the thermosetting resin composition of the present invention, it is preferable that the epoxy compound is an aqueous emulsion and the imide group-containing compound is an aqueous imide group-containing compound.
With such a configuration, the epoxy compound itself, which is a curing component, can be easily handled, and environmental safety can be enhanced. In addition, mixing with an imide group-containing compound or the like as a liquid cross-linking component becomes easy, and by extension, a thermosetting resin composition exhibiting more uniform characteristics can be obtained.

Further, in constructing the thermosetting resin composition of the present invention, the epoxy compound is preferably a novolak epoxy compound.
With this configuration, it becomes easy to make the epoxy compound aqueous (including an emulsion; the same applies hereinafter). Further, if it is a novolak epoxy resin (for example, orthocresol epoxy resin), it is easy to mix it with a predetermined imide group-containing compound, and a thermosetting resin composition exhibiting more uniform properties can be obtained. ..

Further, in constructing the thermosetting resin composition of the present invention, it is preferable that the imide group-containing compound is an imide group-containing compound (partially hydrolyzed product) obtained by partially hydrolyzing a polyimide molded product. ..
With this configuration, an imide group-containing compound obtained by partially hydrolyzing a polyimide molded product also has self-crosslinking property at a low temperature (120 ° C. or lower), and therefore, the obtained cured product has further heat resistance. It can improve the resistance and weather resistance.
Further, 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.

Further, in constituting the thermosetting resin composition of the present invention, the imide group-containing compound is preferably an aqueous imide group-containing compound.
With such a configuration, it becomes easy to mix the aqueous curing component with the epoxy compound, and by extension, an aqueous thermosetting resin composition exhibiting more uniform characteristics can be obtained.
The aqueous 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.

Further, in constructing the 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, the predetermined viscosity stabilizer contributes, and the storage stability of the thermosetting resin composition can be remarkably enhanced.

Further, in constructing the 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. When the total amount of the compounds is 100 parts by weight, the value is preferably in the range of 1 to 300 parts by weight.
With such a configuration, not only the heat resistance and fluidity of the thermosetting resin composition can be easily adjusted, but also the mechanical properties, electrical properties, density and the like of the obtained cured product can be easily adjusted within a desired range. can do.

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. In the reinforcing resin, 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 1-1000000 weight by weight. It is a fiber-reinforced resin characterized by being worthy within the range of the part.
That is, as a binder for a fiber reinforced resin (sometimes referred to as a prepreg before curing), an epoxy compound is used as a curing component, but at least a predetermined amount of a polyimide compound is crosslinked (partially self-crosslinked and cured). By using the 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. 1 (a) explains the influence of the compounding 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. 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. 7A shows the appearance of a fiber reinforced resin (250 ° C., 30-minute cured product) using a thermosetting resin composition, and FIG. 7B shows a thermosetting resin composition using 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, and 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.

[First Embodiment]
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.
Hereinafter, the thermosetting resin composition of the first embodiment will be specifically described for each constituent requirement.

1. 1. Epoxy compound (1) Types The types of epoxy compounds are not particularly limited, and are bisphenol type, diaminodiphenylmethane type, diaminodiphenylsulfone type, aminophenol type, metaxylenediamine type, 1,3-bisaminomethylcyclohexane type, etc. At least one of isocyanurate type, hydantin type, phenol novolak type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylol ethane type and the like can be used.

In particular, it is preferable that the epoxy compound is a novolak epoxy compound (sometimes referred to as an orthocresol novolak type epoxy compound).
The reason for this is that if it is a novolak epoxy compound, it becomes easy to make the epoxy compound aqueous (including an emulsion; the same applies hereinafter).
This is because the epoxy compound and the imide group-containing compound can be easily mixed, and a thermosetting resin composition exhibiting more uniform characteristics can be obtained.

Further, the epoxy compound is preferably an aqueous emulsion.
The reason for this is that the epoxy compound itself, which is 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.
Therefore, as described above, it can be said that the orthocresol novolak epoxy compound is particularly preferable among the epoxy compounds from the viewpoint of making it aqueous.

(2) Number average molecular weight / epoxy equivalent 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.

Further, the epoxy equivalent of the epoxy compound is not particularly limited, but it 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.

2. 2. (1) Type of imide group-containing compound 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.

Therefore, as shown in FIG. 1A, it is possible to exhibit excellent heat resistance in a predetermined thermosetting resin composition.
Here, 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. Further, on the vertical axis, the relative value in the heat resistance evaluation (relative value of the 10% weight loss temperature) based on the TG curve in TG-DTA is taken and shown.
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.

Further, as shown in FIG. 1 (b), the 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.
Here, on the horizontal axis of FIG. 1 (b), the leaving time (up to 5 hours) in the heating furnace is taken every hour, and the retention rate (%) in the leaving time in the cured product containing carbon fiber is shown. 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 after being left at a high temperature of 300 ° C. for 5 hours in the cured product containing carbon fibers. Since there is almost no difference from the value, it is understood that excellent heat resistance is maintained for a long period of time.
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.).

(2) Partial Hydrolyze 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 the partially hydrolyzed product 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 hydrolyzate, one molecule has a plurality of carboxyl groups, amino groups (including amide groups, the same applies hereinafter), hydroxyl groups and the like as functional groups, and epoxy. It can react with the group and can be self-crosslinked by low temperature heating.

Here, FIG. 2 shows an example of an infrared spectroscopic spectrum chart of a partially hydrolyzate 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).
Further, 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 derived from an imide group (peak A) at a wave number of 1375 cm ^-1 and an absorption peak derived from an amide group (peak B) at a wave number of 1600 cm ^-1 . , An imide group-containing compound having an absorption peak (peak C) derived from a carboxyl group at a wave number of 1413 cm ^-1 .
Therefore, in the infrared spectroscopic chart, the imide group-containing compound has an absorption peak (peak D) derived from the carbon of the benzene ring at a wave number of 1500 cm ^-1 and an absorption peak derived from a carbonyl group at a wave number of 1710 cm ^-1 . It has (peak E) and can be used as a reference peak when performing qualitative analysis (specification) of a compound.

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.
The partially hydrolyzed product 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.

In FIG. 4, 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 is 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 indicates that the imide is used. 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% is 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.

Here, when the predetermined functional group of the partial hydrolyzate reacts with the epoxy group of the epoxy compound and is self-crosslinked due to the predetermined functional group, as shown in FIG. 5, the epoxy region (EP) and It is presumed that the polyimide region (PI) causes a microphase separation phenomenon and forms a lamella structure or the like.
Therefore, as a reactant of the epoxy compound / polyimide compound, good heat resistance, adhesion and the like can be exhibited.
Not only that, by including the polyimide compound region bonded to the reaction product of the epoxy compound / polyimide compound at a predetermined position, good heat resistance and weather resistance comparable to that of the polyimide compound alone are exhibited in a well-balanced manner. It is thought that it is.

If it is a hydrolyzed imide group-containing compound, a so-called polyimide molded product can be recycled and used.
Therefore, the cost of producing 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 include, for example, a polyimide film, a polyimide coating, a polyimide resist, a polyimide electric component housing, a polyimide electronic component material, a polyimide container, a polyimide mechanical component, and a polyimide automobile. Examples of the component include a circuit board in which a metal circuit pattern is formed on the surface of a polyimide film, a composite laminate such as TAB tape, and the like.

(3) Average Weight Molecular Weight 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 30,000.
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.

(4) Blending amount The blending amount of the imide group-containing compound is characterized in that the value is in 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 happen.
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 also the mechanical properties and electricity of the obtained cured product. This is because it becomes difficult to adjust the characteristics, density, etc. within a desired range.
Therefore, 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.

(5) Properties The imide group-containing compound is a liquid, and more specifically, an aqueous solvent containing water or alcohol is used as a solvent, and 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.

Further, since the imide group-containing compound can be dissolved in a shorter time, 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, etc. as the aqueous solvent. , For example, 0.1 to 10% by weight) is also preferable.
Examples of such an amine compound include aromatic amines, diamine compounds, aromatic diamines having two amino groups bonded to an aromatic ring and a hetero atom other than the nitrogen atom of the amino group.
More specifically, dimethylaminoethanol, N, N-dimethylbenzylamine, phenylamine (= aniline), N, N-dimethylaniline, N, N-dimethyl-p-toluidine, 2-aminopyridine, tetrahydro-1. , 4-Oxazidin (= morpholine), pyridine, hexahydropyridine (= piperidine), pyrrolidine and the like.
When an amine compound is blended, 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.

3. 3. Solvent (1) Type 1
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.

(2) Type 2
On the other hand, depending on the use of the 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.
Examples of such an organic solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide, N, N-dimethylacetamide, methyldiglime, methyltriglime, dioxane, tetrahydrofuran, cyclohexanone, and cyclo. At least one of pentanone, γ-butyrolactone, toluene, ethyl acetate, butyl acetate, cellosolve, methyl ethyl ketone (MEK), anisole and the like can be mentioned.

(3) Blending amount Regarding the blending amount of the solvent of the thermosetting resin composition, the blending amount of the solvent 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.

More specifically, when 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 may be insufficient, and the handleability may be significantly deteriorated. Because there is.
On the other hand, when the blending amount of the solvent exceeds 99% by weight, the viscosity is excessively lowered, it becomes difficult to form a uniform surface treatment film having a predetermined film thickness, and a precipitate is likely to be formed. 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.

4. Viscosity Stabilizer (1) Type Further, 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, metal ions that are thought to cause pseudo-crosslinking derived from a carboxyl group or a hydroxyl group can be captured and chelated, and high viscosity can be suppressed. Therefore, it has a low viscosity (100 to 100,000 mPsec, measurement temperature 20 ° C.) and can be easily filtered or easily applied.

(2) Blending amount Therefore, the blending amount of the predetermined viscosity stabilizer is preferably a value in 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.

5. Particulate matter (1) type Further, in forming the thermosetting resin composition, it is preferable to further contain at least one particulate matter (including fibrous matter) of carbon particles, inorganic particles and nanoparticles.
The reason for this is that, for example, by including a particulate matter having an average particle size (equivalent to a sphere) of 0.01 to 500 μm, 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 and the like of the obtained cured product can be easily adjusted within a desired range.

More specifically, polyacetylene particles, polyaniline particles, polypyrrole particles, polythiophene particles, nickel particles, silver particles, copper particles, solder particles, silicon oxide, zinc oxide, aluminum oxide, zirconium oxide, titanium oxide, silica nanoparticles, glass nanoparticles. , Ceramic nanoparticles, nanopolyester fiber, nanocellulose fiber, nanopolyamide fiber and the like are preferably blended.

(2) Blending amount The blending amount of the particulate matter is preferably in 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 it becomes difficult to adjust the heat resistance and fluidity of the thermosetting resin composition, but also the mechanical and electrical characteristics of the obtained cured product. This is because it becomes difficult to adjust the density and the like within a desired range.
Therefore, it is more preferable that the blending amount of the particulate matter is in the range of 5 to 80 parts by weight when the total amount of the epoxy compound and the imide group-containing compound is 100 parts by weight, and 10 to 50 parts by weight. It is more preferable that the value is within the range of the unit.

6. Viscosity The viscosity of the 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.

7. Additives In addition, in the 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 improving agent, a dispersant, and a water repellent.
For example, in order to improve the mechanical strength and heat resistance of a thermosetting resin composition, it is possible to add a curing agent or a curing accelerator of an epoxy compound, or a curing agent or a curing accelerator of an imide group-containing compound. However, in that case, 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 to set the value within the range of%.

Further, for example, 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.

Further, for example, in order to improve the storage stability of the thermosetting resin composition and adjust the surface smoothness of the obtained coating film, a predetermined surfactant different from the viscosity stabilizer is used. It is preferable to mix.
In such a case, 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. The value is preferably in the range of 0.01 to 8% by weight, more preferably in the range of 0.1 to 5% by weight, and further preferably 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.

8. Applications The use of the 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. Alternatively, it can also be used as a thermosetting resin composition for impregnating 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.
When 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 use a roll-shaped length in the range of 10 m to 3000 m.

Therefore, the thermosetting resin composition of the first embodiment is a thermosetting resin composition for heat resistance, a thermosetting resin composition for ultraviolet rays resistance, a thermosetting resin composition for high dielectric constant, and a thermosetting resin composition for electrical insulation. It is suitable for at least one of a thermosetting resin composition, a thermosetting resin composition for decorative materials, 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 suitably obtained.

[Second Embodiment]
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, and a reinforcing fiber, which functions at least as a cross-linking component. Therefore, the compounding 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 compounding amount of the reinforcing fiber is set to 1-10000 parts by weight. It is a fiber reinforced resin (including a cured product).
Hereinafter, the fiber-reinforced resin of the second embodiment will be specifically described for each constituent requirement.

1. 1. Epoxy compound Since the epoxy compound as a curing component can have the same contents as described in the first embodiment, the description thereof will be omitted again.

2. 2. 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.

3. 3. Reinforcing fiber (1) Type The type of 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 high-strength nylon fiber, nanofiber, cellac fiber and the like are preferable.
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.

Furthermore, in the case of reinforced fibers such as glass fibers, at least a cured product having more uniform mechanical properties, heat resistance, etc. can be obtained by improving the adhesion to a predetermined thermosetting resin. It is also more preferable to apply a coupling agent treatment, a siliceous flame treatment, a primer treatment and 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 μm.

Then, in order to create a prepreg, it is preferable that the reinforcing fibers are in the form of a sheet.
That is, the morphology 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. ..

Further, it is also preferable to use a plurality of sheet-shaped reinforcing fibers and a plurality of different types of structures in which a nonwoven fabric made of a predetermined resin is sandwiched between them.
In the case of such a multi-layer structure reinforced fiber, the thermosetting resin is uniformly and rapidly injected, particularly through a non-woven fabric, and by extension, the mechanical properties, heat resistance, etc. are more uniform, and a 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). Is typical, but in addition, a plurality of heterogeneous structures formed by sandwiching a non-woven fabric derived from at least one of PET resin, cellulose acetate resin, polyvinyl chloride resin, and polypropylene resin are also preferable.

When the reinforcing fiber is a carbon fiber, 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 the carbon fiber reinforced composite material has a high level of rigidity and strength.
Therefore, the tensile elastic modulus of the carbon fiber more preferably is a value in the range of 230 to 400 GPa, and more preferably a value in the range of 260 to 370 GPa.

Furthermore, it is preferable that 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).
The reason for this is that the sizing treatment improves the adhesion between the thermosetting resin composition and the thermosetting resin composition, and further provides good heat resistance and mechanical properties.

(2) Blending amount 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 does not appear. This is because it may be done.
On the other hand, if the blending amount of the reinforcing fiber exceeds 1,000,000 parts by weight (1,000,000 parts by weight), it becomes difficult to process it into a sheet or uniformly mix the epoxy compound / imide group-containing compound and the reinforcing fiber. 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 further preferably to set the value in the range of 50 to 500 parts by weight.

Hereinafter, the present invention will be described in more detail based on Examples.

[Example 1]
1. 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.

Next, 5 g of the obtained crushed polyimide product, 400 g of ion-exchanged water, and 2 g of potassium hydroxide as a basic substance were contained in a 1000 ml container equipped with a stirrer.
Next, after warming the temperature inside the container to 50 ° C., hydrolysis treatment was carried out under the conditions of 24 hours while stirring the contents to obtain a solution containing a crude imide group-containing compound.

Next, the crude imide group-containing compound is subjected to a series of acid treatment, water washing, alkali treatment, and water washing five times repeatedly to purify the crude imide group-containing compound, and the granular imide group-containing compound (granular imide group-containing compound) is purified. Average particle size: 5 μm).
The granular imide group-containing compound contains 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.

Next, after accommodating 300 g of the aqueous solvent in a container equipped with a stirrer, 100 g of granular (average particle size: 0.3 mm) imide group-containing compound was charged, and a uniform imide group was contained using a stirrer. The mixture was stirred until the compound solution became an aqueous solution.
Next, 100 g of water was additionally added as a diluent for the aqueous solution of the imide group-containing compound, and 8.2 g of triethyl orthoformate was further added as a viscosity stabilizer.

(2) Process (2)
Then, a 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 epoxy compound of the aqueous emulsion (orthocresol novolac resin, manufactured by Japan Epoxy Resin Co., Ltd., product number: W1115 (Table 1, Type 1)). 25 parts by weight of (hydrolyzed imide group-containing compound / compound A) and a predetermined amount of water are mixed, and the mixture is stirred until uniform to make an aqueous thermosetting resin composition (solid content: about 30 weight by weight). %) Was obtained.

(3) Process (3)
The obtained aqueous thermosetting resin composition (solid content: about 30% by weight) is mixed with carbon fibers (Torayca®, T300-) so that the blending ratio is 1000 parts by weight per 100 parts by weight of the epoxy compound. 3K, manufactured by Toray Industries, Inc.) was impregnated to prepare a prepreg.

(4) 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 with 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.

Next, 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).
When 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.

2. 2. Evaluation of Thermosetting Resin Composition and Fiber Reinforced Resin (including Fiber Reinforced Resin Molded Product) (1) 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.
⊚: Colored and transparent, no significant precipitate was observed.
◯: Partially turbid, but no significant precipitate was observed.
Δ: Partially turbid, but a small amount of remarkable precipitate was observed.
X: It becomes turbid and a remarkable precipitate is observed.

(2) Mold formability of fiber reinforced resin (evaluation 2)
The obtained prepreg was molded into the predetermined fiber-reinforced resin shown in FIG. 7A at 200 ° C. and 300 ° C. under the heating conditions of a mold for 60 minutes, respectively, and the appearance thereof was visually inspected according to the following criteria. evaluated.
◯: A predetermined fiber reinforced resin (molded product) having a uniform surface was obtained under the conditions of 300 ° C. × 60 minutes.
Δ: A predetermined fiber reinforced resin (molded product) having a uniform surface was obtained under the conditions of 200 ° C. × 60 minutes.
X: A predetermined fiber reinforced resin (molded product) having a uniform surface could not be obtained under the condition of 200 ° C. × 60 minutes or less.

(3) Adhesion (evaluation 3)
The obtained prepreg was molded using a predetermined mold under heating conditions of 300 ° C. for 60 minutes. Then, a grid test was carried out in accordance with JIS K 5600, and the adhesion between the cured thermosetting resin composition and the reinforcing fiber was evaluated according to the following criteria.
⊚: The number of residual grids is 100/100.
◯: The number of residual grids is 95 or more / 100.
Δ: The number of residual grids is 80 or more / 100.
X: The number of residual grids is less than 80 / 100.

(4) Heat resistance (evaluation 4)
In accordance with JIS K 7120, using a thermal balance (TG-DTA analyzer manufactured by Mettler), heat to 30-500 ° C in a nitrogen stream of 100 ml / min (heating rate 10 ° C / min). A TG-DTA curve was obtained. Then, among the TG-DTA curves, the heat resistance of the obtained polyimide resin film provided with the surface-treated film was evaluated based on the TG curve according to the following criteria.
⊚: The 10% weight loss temperature is 350 ° C. or higher.
◯: The 10% weight loss temperature is 300 ° C. or higher.
Δ: 10% weight loss temperature is 200 ° C. or higher.
X: The 10% weight loss temperature is less than 200 ° C.

[Example 2]
In 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 fiber was impregnated so that the compounding ratio was 10,000 parts by weight per 100 parts by weight.

[Example 3]
In 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 fiber was impregnated so that the compounding ratio was 50,000 parts by weight.

[Example 4]
In Example 4, the blending amount of the imide group-containing compound (partially hydrolyzed product, 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 used as a treca (partial hydrolyzate, compound A). Same as Example 1 except that it is made into M-46J (manufactured by Toray Co., Ltd.) and is impregnated with carbon fiber so that the compounding ratio is 10,000 parts by weight per 100 parts by weight of the epoxy compound. The thermosetting resin composition and the fiber-reinforced resin were evaluated.

[Example 5]
In Example 5, the amount of the imide group-containing compound (partially hydrolyzed product, compound A) to be blended is 300 parts by weight with respect to 100 parts by weight of the epoxy compound in terms of solid content, and the carbon fiber is used as the epoxy compound. Thermosetting resin composition and fiber as in Example 1 except that Treca (registered trademark) and T400-3K (manufactured by Toray Co., Ltd.) are used so that the compounding ratio is 3000 parts by weight per 100 parts by weight. The reinforced resin was evaluated.

[Example 6]
In 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 give 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.
Note that FIG. 8A shows an FT-IR chart of a predetermined imide group-containing compound (compound B before curing).

[Example 7]
In 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).
In addition, 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. Except for using compound C), the thermosetting resin composition and the fiber-reinforced resin were evaluated in the same manner as in Example 1.
Note that FIG. 8B shows an FT-IR chart of a predetermined imide group-containing compound (compound C before curing).

[Example 8]
In Example 8, the types of the epoxy compound as the curing component were 70 parts by weight of a commercially available orthocresol novolak resin (manufactured by Yoshimura Oil Chemical Co., Ltd., product number: KE278) and a bisphenol A type epoxy resin (Dainippon Ink and Chemicals). Example 1 except that 30 parts by weight of a mixture (Type 3 in Table 1) was prepared from "Epoxylon 850" manufactured by Kogyo Co., Ltd. and the amount of the partially hydrolyzed product (Compound A) was 40 parts by weight. Similarly, 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.

As described above, according to the present invention, an epoxy resin as a curing component and an imide group having a specific structure as a cross-linking agent (some of which alone may exert a function as a curing component) are contained. The thermosetting resin composition in which the compound and the compound are blended in a predetermined ratio has not only been excellent in heat resistance and adhesion, but also made it possible to supply the thermosetting resin composition and the like.

Further, according to the present invention, it has become possible to supply a 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, a large amount of the epoxy compound, which is relatively inexpensive per unit weight, is blended, and conversely, the blending amount of the imide group-containing compound, which is relatively expensive per unit weight. It can be said that the higher the amount, the lower the price of the obtained thermosetting resin composition.

Furthermore, in the present invention, if 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.
In addition, a partially hydrolyzed product obtained by partially hydrolyzing a polyimide molded product also has self-crosslinking properties 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.

Claims (8)

Epoxy compounds as curing components and
An imide group-containing compound as a partial hydrolyzate obtained by partially hydrolyzing a polyimide molded product while having a plurality of functional groups capable of reacting with an epoxy group, which at least functions as a cross-linking component.
It is a fiber reinforced resin containing reinforced fibers and
The epoxy compound is an aqueous emulsion, and the imide group-containing compound is an aqueous imide group-containing compound.
The blending amount of the imide group-containing compound was set to a value within the range of 1 to 1000 parts by weight with respect to 100 parts by weight of the epoxy compound.
and,
A fiber-reinforced resin characterized in that the blending amount of the reinforcing fiber is set to a value in the range of 1 to 50,000 parts by weight. The fiber-reinforced resin according to claim 1 , wherein the partially hydrolyzed product has a carboxyl group, an amino group, and a hydroxyl group in an infrared spectroscopic spectrum chart . The fiber-reinforced resin according to claim 1 or 2, wherein the epoxy compound is a novolak epoxy resin. The invention according to any one of claims 1 to 3 , wherein the blending amount of the imide group-containing compound is set to a value within the range of 20 or more and 300 parts by weight or less with respect to 100 parts by weight of the epoxy compound. Fiber reinforced plastic. The fiber-reinforced resin according to any one of claims 1 to 4, wherein the blending amount of the reinforcing fiber is set to a value in the range of 10 to 10,000 parts by weight . The viscosity stabilizer contains at least one of an orthogic acid ester compound, a phytic acid compound, a dacro compound, and EDTA, and the blending amount of the viscosity stabilizer is 100, and the total amount of the epoxy compound and the imide group-containing compound is 100. The fiber-reinforced resin according to any one of claims 1 to 5, wherein the value is in the range of 0.01 to 20 parts by weight. When at least one particulate matter of carbon particles, inorganic particles, and nanoparticles is contained, and the blending amount of the particulate matter is 100 parts by weight, the total amount of the epoxy compound and the imide group-containing compound is 100 parts by weight. The fiber-reinforced resin according to any one of claims 1 to 6, wherein the value is within the range of 300 parts by weight. The fiber-reinforced resin according to any one of claims 1 to 7, wherein the fiber-reinforced resin has a retention rate of 95% by weight or more when left at 300 ° C. for 5 hours in a thermogravimetric reduction test.

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