JPH0977844A - Epoxy resin composition and fiber-reinforced resin tubular article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition comprising an epoxy resin, an epoxy resin- curing agent and a composite rubber-grafted copolymer, having both high toughness and heat resistance, and useful for fiber-reinforced resin tubular articles. SOLUTION: This epoxy resin composition comprises (A) an epoxy resin, (B) an epoxy resin-curing agent, and (c) a composite rubber-grafted copolymer produced by graft-polymerizing (iii) a vinylic monomer to a composite rubber containing (i) a polyorganosiloxane and (ii) a polyalkyl (meth)acrylane. The component C comprises 2-90wt.% of a rubber component containing the component (i) and 10-98wt.% of a rubber component containing the component (ii). The rubber component containing the component (ii) is obtained by polymerizing an aikyl (meth)acrylate, a crosslinking agent such as ethylene glycol dimethacrylate, a grafting agent such as allyl methacrylate, and a graft-crossing agent such as allyl methacrylate. The epoxy resin composition has a structure wherein the rubber component containing the component (i) and the rubber component containing the component (ii) are mutually interlaced so as not to be separated from each other.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition having both high toughness and high heat resistance, and a fiber-reinforced resin tubular body using the same.

[0002]

2. Description of the Related Art Epoxy resins are used in various fields because of their excellent adhesiveness, corrosion resistance, mechanical properties and electrical properties. For example, adhesive, fiber reinforced resin (hereinafter, FR
The matrix resin of P), a sealant for electronic materials, paints, paving materials, etc. can be mentioned. Especially FRP
The matrix resin has been widely used as a high-performance matrix resin.

However, the use of epoxy resin has been limited due to the drawback of low toughness. As a method of imparting toughness to an epoxy resin, a method of adding a rubber component or a thermoplastic resin is generally used, but in order to impart sufficient toughness, a large amount of rubber component or thermoplastic resin must be added. As a result, there is a drawback that the heat resistance is lowered.

[0004]

The present invention solves these technical problems and provides an epoxy resin having excellent toughness and heat resistance, and a fiber-reinforced resin tubular body using the same.

[0005]

That is, the first gist of the present invention is to provide a composite rubber containing (A) an epoxy resin, (B) an epoxy resin curing agent, and (C) a polyorganosiloxane and a polyalkyl (meth) acrylate. The epoxy resin composition comprises a composite rubber-based graft copolymer obtained by grafting a vinyl-based monomer onto a resin, and the second gist is a tubular body composed of a plurality of fiber-reinforced resin layers. The composite rubber system in which the resin forming the resin is a composite rubber containing (A) epoxy resin, (B) epoxy resin curing agent, (C) polyorganosiloxane and polyalkyl (meth) acrylate The fiber-reinforced resin tubular body is an epoxy resin composition comprising a graft copolymer.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A) epoxy resin includes bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetraglycidyl diaminodiphenylmethane, cresol novolac polyglycidyl ether, phenol novolac polyglycidyl ether. Examples thereof include ethers, but the epoxy resin is not limited thereto. It is also possible to use a brominated epoxy resin obtained by bromizing these epoxy resins.

Examples of the epoxy resin curing agent as the component (B) include polyamine curing agents, acid anhydride curing agents, tertiary amine catalyst curing agents, and imidazole catalyst curing agents. The epoxy resin curing agent is not limited to these. The addition amount to the component (A) is appropriately determined depending on the combination of the components (A) and (B) and the target physical properties of the cured product,
There is no particular limitation.

Component (C) is a composite rubber-based graft copolymer obtained by grafting a vinyl-based monomer onto a composite rubber containing a polyorganosiloxane and a polyalkyl (meth) acrylate.

In particular, the rubber component containing polyorganosiloxane is 2 to 90% by weight and the rubber component containing polyalkyl (meth) acrylate is 10 to 98% by weight, and the rubber component containing polyalkyl (meth) acrylate is alkyl. (Meth) acrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate,
A cross-linking agent for polyacrylic (meth) acrylate rubber selected from 1,3-butylene glycol dimethacrylate and 1,4-butylene glycol dimethacrylate, and a polyacryl selected from allyl methacrylate, triallyl cyanurate and triallyl isocyanurate. A structure obtained by polymerizing a graft crossing agent for an alkyl (meth) acrylate rubber, in which a rubber component containing a polyorganosiloxane and a rubber component containing a polyalkyl (meth) acrylate are intertwined with each other so that they cannot be separated from each other. A composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl-based monomers to a composite rubber having an average particle diameter of 0.08 to 0.6 μm is more preferable.

An example of such a composite rubber-based graft copolymer is Metabrene S-20 manufactured by Mitsubishi Rayon Co., Ltd.
No. 01, Metabrene XS-002 and the like can be mentioned, but the invention is not limited thereto.

Component (C) is the most important component in the present invention. This is because the use of the component (C) makes it possible to achieve the goal of the present invention of imparting excellent toughness without lowering the mechanical properties and heat resistance of the cured epoxy resin for the first time. The reason is described below.

Silicon rubber is known as a rubber having excellent impact resistance. However, silicon rubber is generally not well compatible with epoxy resin, and if added as it is, the silicone rubber aggregates (does not disperse), resulting in impact resistance. The effect of improving the sex cannot be obtained. When a compatibilizer is added to disperse silicone rubber in an epoxy resin, heat resistance and mechanical properties often deteriorate, and generally, satisfactory results cannot be obtained. On the other hand, the component (C) of the present invention is a vinyl-based monomer that is relatively compatible with an epoxy resin in a cross-linked composite rubber mainly composed of polyorganosiloxane and polyalkyl (meth) acrylate having excellent impact resistance. Since it is a composite rubber-based graft copolymer having a grafted structure, it is possible to obtain good dispersibility in an epoxy resin, and as a result, it is possible to obtain good dispersibility without sacrificing heat resistance and other mechanical properties. Impact resistance characteristics can be imparted. Further, since it is a crosslinked rubber, the morphology of the cured product does not depend on the curing conditions during the curing process.

There is no problem with the epoxy resin composition of the present invention in that it contains a curing accelerator, an inorganic powder and the like in addition to the components (A), (B) and (C). The mixing method of the component (A), the component (B) and the component (C) is not particularly limited as long as it is a method of dispersing the component (C) in an epoxy resin, but the toughness of the cured resin is more effectively improved. Therefore, it is preferable to release the secondary aggregation of the component (C) and further increase the dispersion. Examples include a method of mixing using a triple roll or a kneader, a method of mixing the component (C) after freeze-grinding, and the like.

The resin composition of the present invention can be impregnated into reinforcing fibers to obtain a prepreg. An FRP molded product molded using the prepreg as an intermediate material can have both good impact properties and good heat resistance.

Examples of the reinforcing fiber of the prepreg include carbon fiber, glass fiber, aramid fiber, alumina fiber and boron fiber, but the fiber is not limited as long as it can be used as the reinforcing fiber of FRP. Not a thing. A preferred application of the epoxy resin of the present invention is a tubular body composed of a plurality of fiber reinforced resin layers such as a golf shaft and a fishing rod. These tubular bodies are often subjected to a strong impact by colliding with an obstacle during use, but by using the epoxy resin of the present invention as a resin forming the fiber-reinforced resin, the Charpy impact strength is significantly improved. Show. Examples of the method for molding the fiber-reinforced resin tubular body of the present invention include, for example, a sheet wrap method in which the above prepreg is wound on a mandrel, and a filament winding method in which the epoxy resin composition of the present invention is wound on the mandrel while impregnating the reinforcing fiber. Further, there may be mentioned a pultrusion molding method in which the reinforcing resin is impregnated with the epoxy resin composition of the present invention and is pulled out through a mold, but it is not particularly limited as long as the tubular body is composed of a plurality of fiber reinforced resin layers.

[0016]

The present invention will be described in detail with reference to the following examples. The evaluation methods in the examples are as follows. (1) "Measurement of energy release rate of cured resin": ASTM
The energy release rate G _IC of the cured resin was determined using a test piece conforming to E399 (TYPE 4A). At this time, a notch was made by applying a cutter blade dipped in liquid nitrogen to the cut portion.

(2) "Measurement of Tg of cured resin": The peak temperature of loss tangent Tan δ measured with a rheometer (RD-700 manufactured by Rheometric Co., Ltd.) at a heating rate of 10 ° C./min is taken as the glass transition temperature Tg of the cured resin. And

(3) "Charpy impact test": Charpy impact tester (IM-105 manufactured by Ueshima, maximum weight: 29.868J, hammer mass: 5.053)
kg, lifting angle: 150 °, impact speed: 3.82 m /
s) was used and the span was measured at 50 mm.

(Synthesis Example 1) Production of a composite rubber graft copolymer (M-1): 2 parts by weight of tetraethoxysilane, 0.5 part by weight of γ-methacryloyloxypropyldimethoxymethylsilane, and octamethylcyclotetrasiloxane. 97.5 parts by weight were mixed to obtain 100 parts by weight of a siloxane mixture. 100 parts by weight of the above-mentioned mixed siloxane was added to 200 parts of distilled water in which 1 part by weight of sodium dodecylbenzenesulfonate and 1 part by weight of dodecylbenzenesulfonic acid were respectively added, and after preliminarily stirring at 10000 rpm with a homomixer, 300 kg / cm ² of a homogenizer was used. It was emulsified and dispersed by pressure to obtain an organosiloxane latex. This mixture was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours while stirring and mixing, and allowed to stand at 20 ° C., and after 48 hours, the pH of the latex was adjusted to 6. with a sodium hydroxide aqueous solution. It was neutralized to 9 and the polymerization was completed to obtain a polyorganosiloxane rubber latex. The polymerization rate of the obtained polyorganosiloxane rubber is 89.7.
%, And the average particle size of the polyorganosiloxane rubber was 0.16 μm.

117 parts by weight of the above polyorganosiloxane rubber latex was sampled, placed in a separable flask equipped with a stirrer, 57.5 parts by weight of distilled water was added, and after nitrogen substitution, the temperature was raised to 50 ° C. -Butyl acrylate 3
A mixed solution of 3.95 parts by weight, 1.05 parts by weight of allyl methacrylate and 0.26 parts by weight of tert-butyl hydroperoxide was charged and stirred for 30 minutes, and this mixed solution was permeated into the polyorganosiloxane rubber particles.

Next, 0.002 parts by weight of ferrous sulfate, 0.006 parts by weight of ethylenediaminetetraacetic acid disodium salt, 0.26 parts by weight of Rongalit and 5 parts of distilled water were charged to initiate a radical reaction, and then, Inner temperature 70
C. for 2 hours to complete the polymerization to obtain a composite rubber latex. A part of this latex was collected and the average particle diameter of the composite rubber was measured to be 0.19 μm. Also, this latex is dried to obtain a solid matter, which is dried with toluene at 90 ° C.
It was extracted for 12 hours, and the gel content was measured and found to be 97.3% by weight. To this composite rubber latex, tert-
Butyl hydroperoxide 0.12 parts by weight and styrene 3
A mixed solution with 0 part by weight was added dropwise at 70 ° C. for 15 minutes and then maintained at 70 ° C. for 4 hours to complete graft polymerization on the composite rubber.

The polymerization rate of styrene was 91.5%.
The obtained graft copolymer latex was dropped into 200 parts by weight of hot water containing 1.5% by weight of calcium chloride, coagulated, separated, washed, and then dried at 75 ° C. for 16 hours to obtain a composite rubber-based graft copolymer ( Hereinafter, referred to as M-1) dry powder of 9
7.8 parts by weight were obtained.

Example 1 100 parts by weight of bisphenol A type epoxy resin Ep828 manufactured by Yuka Shell Epoxy Co., Ltd. was mixed with 10 parts by weight of M-1 in a flask using a three-one motor and a stir bar, and the mixture was mixed with ACI. 4.5 parts by weight of dicyandiamide manufactured by Co., Ltd. and 3,4-dichlorophenyl-N, N manufactured by Hodogaya Chemical Co., Ltd.
-Dimethylurea was mixed with 4 parts by weight to obtain an epoxy resin composition. This is cured under the condition of 130 ℃ × 1 hour,
A cured resin was obtained. The energy release rate G _IC and Tg of this cured resin were measured. The results are shown in Table 1.

(Embodiment 2) In place of M-1 in Embodiment 1, Metabrene S-2001 manufactured by Mitsubishi Rayon Co., Ltd.
A cured resin was obtained in the same manner except that was added. The results of energy release rates G _IC and Tg are shown in Table 1.

(Example 3) Bisphenol A type epoxy resin Ep828100 manufactured by Yuka Shell Epoxy Co., Ltd. was added to Metabrene S-2001 manufactured by Mitsubishi Rayon Co., Ltd.
10 parts by weight were mixed using a triple roll, and 4.5 parts by weight of dicyandiamide manufactured by ACI and 3,4-dichlorophenyl-N, N-dimethylurea 4 manufactured by Hodogaya Chemical Co., Ltd. were added to the mixture. Parts by weight were mixed in the flask using a three-one motor and a stir bar. This one
It was cured under the conditions of 30 ° C. × 1 hour to obtain a cured resin. Energy release rate G _IC and Tg of this cured resin
Was measured. The results are shown in Table 1.

Comparative Example 1 A cured resin was obtained in the same manner as in Example 1 except that M-1 was not added. The results of energy release rates G _IC and Tg are shown in Table 1.

(Comparative Example 2) 62.5 parts by weight of rubber-modified epoxy resin TSR960 manufactured by Dainippon Ink and Chemicals, Inc. and 47.5 parts by weight of bisphenol A type epoxy resin Ep828 manufactured by Yuka Shell Epoxy Co., Ltd. were used in a flask. The mixture was mixed using a motor and a stirring rod, and 4.5 parts by weight of dicyandiamide manufactured by ACI Co., Ltd. and 4 parts by weight of 3,4-dichlorophenyl-N, N-dimethylurea manufactured by Hodogaya Chemical Co., Ltd. were added to the mixture. An epoxy resin composition was obtained by mixing in a flask using a three-one motor and a stirring rod. This was cured at 130 ° C. for 1 hour to obtain a cured resin. The results of energy release rates G _IC and Tg are shown in Table 1.

(Example 4) Bisphenol A type epoxy resin Ep82842 manufactured by Yuka Shell Epoxy Co., Ltd. was added to Metabrene S-2001 manufactured by Mitsubishi Rayon Co., Ltd.
10 parts by weight were mixed using a three-roll, and the mixture and 58 parts by weight of bisphenol A type epoxy resin Ep1001 manufactured by Yuka Shell Epoxy Co., Ltd. in a flask, 50
The mixture was mixed at 3 ° C using a three-one motor and a stir bar. Further, 4.5 parts by weight of dicyandiamide manufactured by ACI Co., Ltd. and 4 parts by weight of 3,4-dichlorophenyl-N, N-dimethylurea manufactured by Hodogaya Chemical Co., Ltd. were placed in a flask.
Mix at 50 ° C. using a Three One motor and stir bar. This was cured at 130 ° C. for 1 hour to obtain a cured resin. Energy release rate G for this cured resin
_IC and Tg were measured. The results are shown in Table 1.

Comparative Example 3 A cured resin was obtained in the same manner as in Example 4 except that Methbrene S-2001 was not added. The results of energy release rates G _IC and Tg are shown in Table 1.

Example 5 Yuka Shell Epoxy Co., Ltd. Bisphenol A type epoxy resin Ep82842 parts by weight was mixed with M-1 and 10 parts by weight using a three-roll mill, and the mixture and the oiled shell epoxy stock were mixed. 58 parts by weight of Ep1001 made of bisphenol A type epoxy resin of the company was mixed in a flask at 50 ° C. using a three-one motor and a stirring rod. Further, 6 parts by weight of dicyandiamide manufactured by ACI Corporation was mixed. This resin was made into a film having a basis weight of 74 g / m ² using a film coater.

Carbon fiber Pyrofil MR50 manufactured by Mitsubishi Rayon Co., Ltd. having a fiber areal weight of 15 is applied on the above film resin.
Arrange in one direction so that it will be 0 g / m ² and heat press (80
The reinforcing fiber was impregnated with the resin at 2 ° C., 2 kg / cm ² ) to obtain a prepreg.

On the 10φ mandrel, the above prepreg was + 45 ° / −45 ° / + 45 ° / −45 ° / 0 from the inner layer.
Laminated in a laminated constitution of ° / 0 ° / 0 ° and cured at 130 ° C for 1 hour to prepare a carbon fiber reinforced resin tubular body.

A Charpy impact test was conducted on the carbon fiber reinforced resin tubular body to obtain a Charpy impact value. The results are shown in Table 1 together with the Tg of the cured resin.

(Example 6) In Example 5, instead of M-1, Metabrene S-2001 manufactured by Mitsubishi Rayon Co., Ltd.
A carbon fiber reinforced resin tubular body was produced in the same manner except that was used, and a Charpy impact test was performed. The results are shown in Table 1 together with the Tg of the cured resin.

Example 7 In place of M-1 in Example 5, Metabrene XS-002 manufactured by Mitsubishi Rayon Co., Ltd.
A carbon fiber reinforced resin tubular body was produced in the same manner except that was used, and a Charpy impact test was performed. The results are shown in Table 1 together with the Tg of the cured resin.

Comparative Example 4 A carbon fiber reinforced resin tubular body was prepared in the same manner as in Example 5 except that M-1 was not added, and a Charpy impact test was conducted. The result is T of cured resin
It is shown in Table 1 together with g.

(Comparative Example 5) 62.5 parts by weight of rubber-modified epoxy resin TSR960 manufactured by Dainippon Ink and Chemicals, Inc. and 47.5 parts by weight of bisphenol A type epoxy resin Ep1001 manufactured by Yuka Shell Epoxy Co., Ltd. in a flask, 50 The mixture was mixed at 3 ° C using a three-one motor and a stir bar. Further, 6 parts by weight of dicyandiamide manufactured by ACI Corporation was mixed. This resin was made into a film having a basis weight of 74 g / m ² using a film coater.

A carbon fiber reinforced resin tubular body was prepared in the same manner as in Example 5 and subjected to a Charpy impact test. The results are shown in Table 1 together with the Tg of the cured resin.

[0039]

[Table 1]

[0040]

According to the present invention, an epoxy resin composition having both high toughness and high heat resistance can be obtained. A fiber-reinforced resin tubular body using it as a matrix resin has high Charpy impact strength.

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Claims (3)

[Claims] 1. A composite rubber system obtained by grafting a vinyl monomer onto a composite rubber containing (A) epoxy resin, (B) epoxy resin curing agent, (C) polyorganosiloxane and polyalkyl (meth) acrylate. An epoxy resin composition comprising a graft copolymer. 2. The composite rubber-based graft copolymer of (C) comprises 2 to 90% by weight of a rubber component containing polyorganosiloxane and 10 to 98% by weight of a rubber component containing polyalkyl (meth) acrylate. Polyalkyl (meta)
The rubber component containing acrylate is a polyacrylic (meth) selected from alkyl (meth) acrylate and ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate and 1,4-butylene glycol dimethacrylate. A polymer obtained by polymerizing a cross-linking agent for acrylate rubber and a graft-linking agent for polyalkyl (meth) acrylate rubber selected from allyl methacrylate, triallyl cyanurate and triallyl isocyanurate, and containing polyorganosiloxane. One or more vinyl-based monomers are added to a composite rubber having an average particle diameter of 0.08 to 0.6 μm and having a structure in which the rubber component and the rubber component containing polyalkyl (meth) acrylate are intertwined with each other so that they cannot be separated. Graft The combined and a composite rubber-based graft copolymer comprising Claim 1 epoxy resin composition. 3. A tubular body comprising a plurality of fiber reinforced resin layers, wherein the resin forming the fiber reinforced resin is (A) epoxy resin, (B) epoxy resin curing agent, (C) polyorganosiloxane and polyalkyl. A fiber-reinforced resin tubular body which is an epoxy resin composition comprising a composite rubber-based graft copolymer obtained by grafting a vinyl-based monomer onto a composite rubber containing (meth) acrylate.