WO2011039879A1

WO2011039879A1 - Matrix resin composition for fiber-reinforced plastics, and fiber-reinforced plastic structures

Info

Publication number: WO2011039879A1
Application number: PCT/JP2009/067147
Authority: WO
Inventors: 有重成; 裕之佐藤; 敬原田
Original assignee: 株式会社Ｉｈｉエアロスペース; 株式会社Ihi
Priority date: 2009-10-01
Filing date: 2009-10-01
Publication date: 2011-04-07
Also published as: WO2011040567A1; JPWO2011040567A1

Abstract

Provided are: a matrix resin composition for fiber-reinforced plastics which can yield fiber-reinforced plastics having excellent shock-absorbing properties; and fiber-reinforced plastic structures. A matrix resin composition for fiber-reinforced plastics, which comprises 20 to 100 parts by weight of (A) a bisphenol-based epoxy resin, 0 to 80 parts by weight of (B) a modified epoxy resin, 0 to 80 parts by weight of (C) a polyfunctional epoxy resin, and (D) a curing agent, and further contains (E) elastically deformable particles having a mean particle diameter of 0.01 to 0.5μm in an amount of 1 to 50 parts by weight per 100 parts by weight of the total amount of the components (A) to (C), with the proviso that the elastically deformable particles (E) are such particles that can be dispersed and kept in a suspended state in a cured product prepared from the components (A) to (E).

Description

Matrix resin composition for fiber reinforced plastic and fiber reinforced plastic structure

The present invention relates to a matrix resin composition for fiber reinforced plastic and a fiber reinforced plastic structure having improved impact absorption.

Conventionally, a metal material such as a titanium alloy has been used for impact resistant parts such as a fan case of an aircraft jet engine as shown in FIG.
In recent years, the demand for engine weight reduction tends to increase due to soaring fuel costs.
However, in aircraft impact-resistant parts that require safety, there is a limit to the weight reduction of metal parts due to their characteristics.

As a substitute for metal parts, fiber-reinforced plastic materials are attracting attention. Fiber reinforced plastic has been developed for many years as a material for aircraft parts such as a fan case of a jet engine (for example, Patent Document 1).

JP 2006-305867 A

In recent years, application of fiber reinforced plastics to aviation parts such as aircraft bodies has been progressing. However, as for the application to jet engine parts among aviation parts, since severe characteristics such as impact resistance and heat resistance are required, the application of fiber reinforced plastics is currently limited.
For example, a fan case is required to have impact resistance per unit weight, but the impact resistance per unit weight of a conventional fiber reinforced plastic is equal to or inferior to that of a metal material. As a result, even if a fiber reinforced plastic material is used, it has not been reduced in weight so as to improve fuel efficiency as compared with a fan case using a metal material.

The present invention has been made in view of such problems of the prior art, and the object of the present invention is to provide a matrix resin composition for fiber reinforced plastic and a fiber reinforced plastic structure having excellent shock absorption. Is to provide.

As a result of intensive studies to achieve the above object, the present inventors have suspended the above particles in a cured product in which an epoxy resin, a curing agent, and elastically deformable particles having a specific average particle diameter are mixed. It has been found that the above object can be achieved by being dispersed and held in a turbid state.

That is, the present invention comprises (A) 20 to 100 parts by weight of a bisphenol-based epoxy resin, (B) 0 to 80 parts by weight of a modified epoxy resin, (C) 0 to 80 parts by weight of a polyfunctional epoxy resin, (D 1) to 50 parts by weight of the curing agent and (E) elastically deformable particles having an average particle diameter of 0.01 to 0.5 μm with respect to 100 parts by weight of the total amount of the above (A) to (C). A matrix resin composition for fiber-reinforced plastic in which the particles (D) are dispersed and held in a suspended state in the cured product containing the above (A) to (E).

Further, the present invention is a fiber reinforced plastic structure using the matrix resin composition for fiber reinforced plastic.

Furthermore, the present invention is an aircraft engine part using the fiber reinforced plastic structure.

According to the matrix resin composition for fiber-reinforced plastics of the present invention, particles having an epoxy resin, a curing agent, and a specific average particle diameter, a sufficiently low elastic modulus as compared with the epoxy resin, and being elastically deformable even in the epoxy resin Since the particles are dispersed and held in a suspended state in the cured product in which is mixed, high impact absorbability can be expressed.
Since the fiber reinforced plastic structure of the present invention can exhibit high shock absorption, it can be suitably used for aircraft parts such as fan cases, fan blades, and fan frames of jet engines.

It is a schematic fragmentary sectional view which cut and shows a part of fan case which is an example of the aircraft engine components by this invention.

Hereinafter, components (A) to (E) and other optional components constituting the matrix composition for fiber-reinforced plastic of the present invention will be described in detail below.
In the present specification, “%” such as yield represents a mass percentage unless otherwise specified.

[Component (A)]
The component (A) used in the present invention is a bisphenol epoxy resin.
Examples of the bisphenol-based epoxy resin include a bisphenol A type epoxy resin having an epoxy equivalent of 200 or less, a bisphenol F type epoxy resin having an epoxy equivalent of 200 or less, a solid bisphenol A type epoxy resin having an epoxy equivalent of about 400 to 2500, an epoxy equivalent And a solid bisphenol F type epoxy resin having a viscosity of about 400 to 2500. These may be used alone or in combination of two or more.
Among them, it is preferable to use a bisphenol A type epoxy resin having an epoxy equivalent of 200 or less, a bisphenol F type epoxy resin having an epoxy equivalent of 200 or less, and a mixture thereof.

The blending ratio of the component (A) bisphenol-based epoxy resin is 20 to 100 parts by weight, preferably 30 to 90 parts by weight, more preferably 40 to 40 parts by weight based on 100 parts by weight of the total of components (A) to (C). 80 parts by weight, more preferably 50 to 80 parts by weight.
When the blending ratio of component (A) exceeds 90 parts by weight, the crosslink density of the cured resin is increased and the glass transition temperature (Tg), which is an index of heat resistance, is increased, but the toughness of the cured resin is decreased. Absent.
On the other hand, when the blending ratio of component (A) is less than 20 parts by weight, the blending ratio of component (B) and component (C) increases, the viscosity of the mixture increases, and the flexibility of the precursor of the fiber reinforced plastic increases. Decreases, and workability at the time of stacking deteriorates, which is not preferable.

[Component (B)]
Component (B) used in the present invention is a modified epoxy resin.
Examples of the modified epoxy resin include a bifunctional epoxy resin having a naphthalene skeleton and a phenoxy resin having a hydroxyl group in the molecule.
As the component (B), one or more of the modified epoxy resins can be used in combination.

The blending ratio of the component (B) modified epoxy resin is 0 to 80 parts by weight, preferably 2 to 80 parts by weight, more preferably 2 to 50 parts per 100 parts by weight of the total of components (A) to (C). Part by weight, more preferably 2 to 30 parts by weight.
When the blending ratio of component (B) exceeds 80 parts by weight, it is preferable because the crosslink density of the cured resin increases and the glass transition temperature (Tg), which is an index of heat resistance, increases, but the toughness of the cured resin decreases. Absent.
In the case where heat resistance characteristics are not taken into consideration, the blending ratio of the component (B) modified epoxy resin may be 0 parts by weight.

[Component (C)]
Component (C) used in the present invention is a polyfunctional epoxy resin.
Examples of the polyfunctional epoxy resin include triglycidylparaaminophenol, tetraglycidylaminomethane, and a novolac type epoxy resin.
As the component (C), one or more polyfunctional epoxy resins can be used in combination.

The blending ratio of the polyfunctional epoxy resin of component (C) is 0 to 80 parts by weight, preferably 2 to 80 parts by weight, more preferably 2 parts per 100 parts by weight of the total of components (A) to (C). -50 parts by weight, more preferably 2-30 parts by weight.
When the blending ratio of component (C) exceeds 80 parts by weight, it is preferable because the crosslink density of the cured resin increases and the glass transition temperature (Tg), which is an index of heat resistance, increases, but the toughness of the cured resin decreases. Absent.
When heat resistance characteristics are not taken into consideration, the blending ratio of the polyfunctional epoxy resin of component (C) may be 0 part by weight.

[Component (D)]
Component (D) used in the present invention is a curing agent.
As the curing agent, generally known amine curing agents, acid anhydride curing agents, phenol curing agents and the like can be used. In addition, catalyst curing agents such as imidazole and boron trichloride-based amine complexes can be used.
Especially, since it is known from the test results that the amine-based curing agent can improve the shock absorption, it is preferable to use an amine-based curing agent as the curing agent.
When the curing agent of component (D) is a toughness imparting agent, benzenediamine, diaminodimethylmethane, methanephenylenediamine and the like can be used.
Component (D) can be used by mixing one or more of the above curing agents.

Component (D) curing agent is blended so as to have a blending ratio that completely reacts with components (A) to (C). Specifically, the curing agent of component (D) is blended so as to be equivalent to the epoxy groups contained in the epoxy resins of components (A) to (C) (equal molar ratio).

In the above component (D), a small amount of salicylic acid, boron trifluoride ethylamine complex or the like may be added for adjusting the reaction rate during curing.

[Ingredient (E)]
Component (E) is an elastically deformable particle having an average particle size of 0.01 to 0.5 μm, preferably 0.05 to 0.2 μm.
When the average particle diameter of the elastically deformable particles of the component (E) is larger than 0.5 μm, the particles of the component (E) are dispersed in a cured state containing the components (A) to (E). It cannot be held.
In the present specification, the elastically deformable particles of the component (E) are dispersed and held in the cured products of the components (A) to (E) to mean the elastic deformation of the component (E). The possible particles are dispersed and held in the cured product, completely phase-separated from the other components without being compatible with the other components (components (A) to (D)) constituting the cured product. Means that.

The component (E) is not particularly limited as long as it is an elastically deformable particle having the above average particle diameter, but is selected from the group consisting of polybutadiene rubber, styrene butadiene rubber, and butyl rubber. In addition, it is preferable to contain one or a mixture of two or more.
As the component (E), particles in which elastically deformable particles containing the rubber material as described above are dispersed in an epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin may be used.

The elastically deformable particles of component (E) may have a core-shell structure consisting of a core portion and a shell layer surrounding it.
As a material constituting the particles having a core-shell structure, the core portion contains at least one selected from the group consisting of polybutadiene rubber, styrene butadiene rubber and butyl rubber, and the shell layer contains vinyl chloride and / or acrylic resin. It is preferable that

The blending ratio of the elastically deformable particles of the component (E) is 1 to 50 parts by weight, preferably 2 to 30 parts by weight, more preferably 100 parts by weight of the total amount of the components (A) to (C). 2 to 25 parts by weight, particularly preferably 2 to 15 parts by weight.
When the blending ratio of the particles of component (E) is less than 1 part by weight with respect to 100 parts by weight of the total amount of components (A) to (C), a cured product (cured product of matrix composition) upon impact load This reduces the effect of reducing the progress of cracks that occur.
On the other hand, when the blending ratio of component (E) exceeds 50 parts by weight with respect to 100 parts by weight of the total amount of components (A) to (C), in the mixture containing components (A) to (E) Suspension and dispersibility are reduced.
When the component (E) is used in which elastically deformable particles are dispersed in an epoxy resin or the like, the blending ratio of the elastically deformable particles is the total amount of the components (A) to (C). The blending ratio of the epoxy resin in which the elastically deformable particles are dispersed may not be considered as long as it is within the above range with respect to 100 parts by weight.

The matrix resin composition for fiber-reinforced plastics of the present invention comprises (A) 20 to 100 parts by weight of a bisphenol-based epoxy resin, (B) 0 to 80 parts by weight of a modified epoxy resin, and (C) a polyfunctional epoxy resin. 0 to 80 parts by weight, (D) a curing agent, and (E) 1 to 50 parts by weight of elastically deformable particles having an average particle diameter of 0.01 to 0.5 μm, and the above (A) to (E) Since the above (E) particles are dispersed and held in a suspended state in the cured product containing, high impact absorbability can be expressed.

The fiber reinforced plastic structure of the present invention uses the above matrix resin composition for fiber reinforced plastic.
As a method for producing a fiber-reinforced plastic structure, a reinforcing fiber can be impregnated with the matrix resin composition and cured to obtain a structure made of a cured product of a specific form.

Examples of reinforcing fibers include glass fibers, carbon fibers, aramid fibers, alumina fibers, and boron fibers. Among them, carbon fiber is preferably used because it has excellent properties of high strength and high elastic modulus while being lightweight.

As the reinforcing fiber, either a short fiber or a long fiber can be used. When placing importance on mechanical properties such as mechanical strength, it is preferable to use long fibers (for example, a length of 10 cm or more), and when placing importance on formability, short fibers (for example, a length of 10 cm or less). Is preferably used.

As the arrangement structure of the reinforcing fibers, any arrangement structure such as a single direction, two directions, and a random direction can be used, and a woven fabric and a knitted fabric of reinforcing fibers can also be used.
In order to further improve the shock absorption, it is preferable to use a woven fabric of reinforcing fibers.

Since the fiber reinforced plastic structure of the present invention uses a matrix resin composition capable of exhibiting high impact absorption, an impact resistant part for aircraft, for example, as shown in FIG. The present invention can be suitably used for fan cases, fan blades, fan frames, etc. of aircraft jet engines as shown.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

The following materials were prepared as components (A) to (E).
[Component (A)]
(A-1) jer806; bisphenol F type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)
(A-2) jer807: Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)
(A-3) jer1001; bisphenol A type solid epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)
(A-4) jer4004P; bisphenol F type solid epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)

[Component (B)]
(B) HP4032; naphthalene skeleton-containing epoxy resin (Dainippon Ink Chemical Co., Ltd.)

[Component (C)]
(C) jer604; tetrafunctional epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)

[Component (D)]
(D-1) jerW: amine-based curing agent (manufactured by Japan Epoxy Resin Co., Ltd.)
The (D-1) curing agent functions as a toughness imparting agent.
(D-2) EK150D; DDM (diaminodiphenylmethane) (manufactured by Japan Epoxy Resin Co., Ltd.)

[Ingredient (E)]
In the examples, the elastically deformable particles composed of the following rubber components were previously contained in the epoxy resin. The particles contained in the following (E-1) to (E-3) all had an average particle diameter of 0.01 to 0.5 μm.
(E-1) Bisphenol A type epoxy resin (manufactured by Kaneka Corporation) containing 25 wt% of styrene butadiene rubber particles (elastically deformable particles)
(E-2) Bisphenol F type epoxy resin (manufactured by Kaneka Corporation) containing 25 wt% of polybutadiene rubber particles (elastically deformable particles)
(E-3) Bisphenol A type epoxy resin (manufactured by Kaneka Corporation) containing 25 wt% of polybutadiene rubber particles (elastically deformable particles)

The following compounds were prepared as other components used in the comparative example.
Acid anhydride curing agent: MHAC-P (Methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride) (manufactured by Hitachi Chemical Co., Ltd.)
・ Catalyst: EHC-30 (Tertiary amine catalyst) (Adeka)
-Latent curing agent: DY9577 (boron trichloride amine complex) (manufactured by HUNTSMAN)
-Latent curing agent: 2E4MZ (2-ethyl-4-methylimidazole) (manufactured by Shikoku Chemicals)

Table 1 shows the product names and composition of the above components (A) to (E) and other components.
The matrix resin composition blended as shown in Table 1 was impregnated into carbon fiber trading card (registered trademark) T (800S-24K (manufactured by Toray Industries, Inc.) to a resin content of 36% by mass by a solvent method. A precursor of reinforced plastic (FRP) was formed and quasi-isotropically laminated.
Incidentally, the pseudo-temporal isotropic lamination usually means a layer having a fiber orientation of 0 °, 90 °, 45 °, and −45 ° with respect to a reference direction.
A pseudo-isotropic laminate of FRP precursors was cured in a 0.6 MPa autoclave at 100 ° C. for 2 hours, then at 120 ° C. for 1 hour, and finally at 180 ° C. for 6 hours to obtain a length of 200 mm × width of 150 mm X An FRP flat plate having a thickness of 5 mm was obtained.

[Evaluation methods]
Titanium bullets with a diameter of 10 mm x length of 12 mm are shot at a speed of 100 to 250 m / sec with a hunting gun on the surface of the FRP flat plate formed with the composition shown in Table 1, and the bullet velocity before and after penetration of the FRP flat plate Was measured with a high-speed camera, and the rate of speed decrease before and after the collision was calculated by the following equation (1), and evaluated as impact absorbability. The results are shown in Table 1.
Evaluation formula for impact resistance:
Impact absorption rate (%) = speed after impact penetration (m / second) / speed before impact (m / second) × 100 (1)

As shown in Table 1, FRP flat plates using the matrix resin compositions of Examples 1 to 12 had a high impact absorption rate of 65% or more.
On the other hand, as shown in Table 2, the impact absorptivity of the FRP flat plates of Comparative Examples 1 to 5 not containing the elastically deformable particles of the component (E) was 55% or less.
In the comparative examples, the FRP flat plates of Comparative Examples 1 and 2 using a matrix resin composition containing an amine curing agent have a relatively high impact absorption rate of 50% or more, whereas amine-based curing. The impact absorption rates of Comparative Examples 3 to 5 using a curing agent other than the agent were as small as 32% or less.

According to the matrix resin composition for fiber-reinforced plastic of the present invention, (A) 20-100 parts by weight of bisphenol-based epoxy resin, (B) 0-80 parts by weight of modified epoxy resin, (C) polyfunctional epoxy Containing 0 to 80 parts by weight of resin, (D) a curing agent, and (E) 1 to 50 parts by weight of elastically deformable particles having an average particle size of 0.01 to 0.5 μm. Since the particles (E) are dispersed and held in a suspended state in the cured product containing E), high impact absorbability can be expressed.
The fiber reinforced plastic structure using the matrix resin composition has an impact resistance per unit weight that is 1.5 times as excellent, and can be reduced in weight compared to a metal material.
As described above, the fiber reinforced plastic structure of the present invention is excellent in shock-absorbing property, so that safety can be ensured and the weight can be reduced. For example, an aircraft jet as shown in FIG. It can be suitably used for engine fan cases, fan blades, fan frames, and the like, and its industrial utility value is extremely high.

Claims

(A) 20 to 100 parts by weight of a bisphenol-based epoxy resin,
(B) 0 to 80 parts by weight of the modified epoxy resin,
(C) 0 to 80 parts by weight of a polyfunctional epoxy resin,
(D) a curing agent,
Furthermore, (E) 1 to 50 parts by weight of elastically deformable particles having an average particle diameter of 0.01 to 0.5 μm are contained with respect to 100 parts by weight of the total amount of the above (A) to (C),
A matrix resin composition for fiber-reinforced plastic, wherein the particles (E) are dispersed and held in a suspended state in a cured product containing the above (A) to (E).
2. The matrix resin composition for fiber-reinforced plastics according to claim 1, wherein the (E) particles contain at least one selected from the group consisting of polybutadiene rubber, styrene butadiene rubber and butyl rubber.
The (E) particles have a core-shell structure consisting of a core portion and a shell layer surrounding the core portion, and the core portion contains at least one selected from the group consisting of polybutadiene rubber, styrene butadiene rubber and butyl rubber The matrix resin composition for fiber reinforced plastics according to claim 1 or 2, wherein the shell layer contains a vinyl chloride resin and / or an acrylic resin.
The particle (E) is contained in an amount of 2 to 30 parts by weight with respect to 100 parts by weight of the total amount of (A) to (C). Matrix resin composition for fiber reinforced plastics.
The matrix resin composition for fiber-reinforced plastics according to any one of claims 1 to 4, wherein the (D) curing agent is an amine curing agent.
The matrix resin composition for fiber-reinforced plastics according to any one of claims 1 to 5, wherein the (D) curing agent is a toughness imparting agent.
A fiber reinforced plastic structure using the matrix resin composition for fiber reinforced plastic according to any one of claims 1 to 6.
An aircraft engine part using the fiber-reinforced plastic structure according to claim 7.