JPS60250026A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:An epoxy resin composition having high heat resistance and excellent impact resistance and excellent water resistance, prepared by mixing or pre- reacting an epoxy resin with a polysulfone resin and a specified polyfunctional compound. CONSTITUTION:The titled composition prepared by mixing or pre-reacting 100pts.wt. epoxy resin with 5-30pts.wt. polysulfone resin (e.g., thermosetting polysulfone resin comprising recurring unit groups of the formula and obtained by reacting these groups with epichlorohydrin at an OH/Cl ratio <1.0), and at least one compound selected from the group consisting of (a) a polymaleimide [e.g., bis(4-maleimidophenyl)methane], (b) a polycyanate ester [e.g., 2,2-bis(4- cyanatophenyl)propane] and (c) a prereaction product between compounds (a) and (b). This epoxy resin composition has high heat resistance and excellent impact resistance and water resistance and can exhibit excellent performance especially as a matrix resin for a composite material with carbon fiber or the like.

Description

[Detailed description of the invention] 〔Technical field〕 The present invention relates to a novel epoxy resin composition.

[Background technology]

Epoxy resins are generally cured by combining a curing agent and a curing accelerator and heating them.
Because of its excellent thermal and electrical characteristics, it is widely used in adhesives, cast products, paints, molded products, laminated products, etc.
It's being used.

In recent years, in these various applications, there has been a strong demand for higher performance of cured epoxy products, especially improvements in heat resistance, impact resistance, water resistance, etc., and intensive research is being carried out to meet these demands. . Especially when used as a matrix resin for composite materials, the above-mentioned performances of the composite are:
This is thought to be due to the matrix resin, and depending on the application, for example, in the field of primary structural materials such as aircraft, it is required that these various performances be excellent overall.

Currently, when particularly heat resistance is required, polyfunctional epoxy resins such as N, N, and N' are used as epoxy resins.

N'-tetraglycidyldiaminodiphenylmethane, 1
, 1,2.2-tetraglycidylphenolethane, N
, N-diglycidyl-m-phenylglycidyl ether, N,N',N'-)liglycidyl in cyanurate, etc. are used as the main components, and these are generally used singly or in combination of two or more. It is used in combination with aromatic amines such as -diaminodiphenylsulfone and 3,3'-diaminodiphenylsulfone. However, these cured heat-resistant epoxy resins generally have low impact resistance and water resistance (which has been considered a serious drawback).

As a method to improve the impact resistance of cured epoxy resin products,
Resin system containing thermoplastic polysulfone resin
No. 17067, No. 48-5107, etc.), but since Gore et al.'s method contains the polysulfone resin as a thermoplastic resin, the cured resin composition has insufficient heat resistance. However, it also had the disadvantage of poor solvent resistance. In addition, as a method to improve water resistance, 1
, 1,2,2-tetraglycidylethane (JP-A-58-1718) has been proposed, but problems regarding impact resistance still remain.

[Purpose of the invention]

In view of the current situation, the inventors of the present invention have arrived at the present invention as a result of carrying out a study on the amount of epoxy resin compositions that have high heat resistance and excellent impact resistance and water resistance.

[Structure of the invention]

That is, the gist of the present invention is that [A] epoxy resin CB] polysulfo/resin [C] polyfunctional maleimides (1), polyfunctional cyanate esters (...), and the above (1) and (It ) is an epoxy resin composition obtained by mixing or preliminarily reacting with at least one selected from the group consisting of prereactants, and particularly contains a repeating unit group as a polysulfo/resin,
The resin composition selected is a thermosetting polysulfone resin obtained by reacting with an shrimp chlorohydrin 0H7cl ratio of less than 1.0.

The epoxy resin used in the present invention is the polyfunctional epoxy resin described above, ie, N, N, N', N'-tetraglycidyldiaminodiphenylmethane, 1.1, 2.
2-tetraglycidylphenolethane, N,N-diglycidyl-m-aminophenylglycidyl ether, N
, N', N"-triglycine ruin cyanurate, etc. These epoxy resins can be used alone or in a mixture of 28i or more. These epoxy resins are used in combination with a curing agent. However, the curing agent used in the present invention is an aromatic polyamine from the viewpoint of heat resistance.

Specifically, for example, 4,4'-diaminodiphenylsulfo7.3.3'-diaminodiphenylsulfo/, m-7
Examples include 1-2-cyamine, 2,4-)luenediamine, and the like.

The polysulfone resin used in the present invention must be a thermosetting polysulfone/resin.

The thermosetting polysulfone resin has the general formula H as described below.
O+A-So, polysulfone resin containing a repeating unit group represented by OH and shrimp chlorhydride/0H7c
It can be obtained by reacting at a l ratio of less than 1.0. The polysulfo/resin is not particularly limited as long as it has the general formula %, but examples include those having the following structural formula including -A-.

These polysulfone/resins must have an OH group as a terminal group, and can be made into a thermosetting polysulfone resin by reaction with epichlorohydrin. The molecular weight of the polysulfo/resin is not limited to %, but from the viewpoint of mechanical properties of the cured resin product obtained by the present invention, it is preferably n=2 or more. Among the above polysulfone resins, for example, HO+C o-0so, %OOH is polyethersulfone VICTREX 100p (trademark manufactured by ICI)
It is commercially available at ℃. The thermosetting polysulfone resin used in the present invention can be obtained by reacting the polysulfone/resin described above with an appropriate stoichiometric amount of epichlorohydrin in the presence of an alkali by a known method. The stoichiometry is important here, and it is necessary to react the polysulfone resin and shrimp chlorhydride at an 0H7cl ratio of less than 1.0. When the OH/Cl ratio exceeds 1.0, OH groups remain, resulting in not only insufficient light and heat resistance but also poor water resistance and solvent resistance.

It should be noted that the term ``ideal'' here means stoichiometry, in which one OH group is equivalent to one CJ group.

The polyfunctional maleimides (1) used in the present invention include bismaleimides having two or more maleimide groups derived from maleic anhydride and diamide/and represented by the general formula (2) % formula %; These include prepolymers obtained from bismaleimides.

The above-mentioned bismaleimide can be produced by a known method in which maleic anhydride and diamines are reacted to prepare bismanoamic acid, and then cyclized by dehydration.

The diamine used is preferably an aromatic diamine from the viewpoint of heat resistance, which is the objective of the present invention, but if it is desired to impart functions such as flexibility, aliphatic amines may be used alone or in combination. is also possible. Examples of specific diamines are Idm-phenylenediamine, p-phenylenediamine, 4.4'-diaminodiphenylsulfone, 3.3'-diaminodiphenylsulfo/, 4°4'
Typical examples include -diaminodiphenylmethane and 4,4'-diaminodiphenyl ether.

Polyfunctional cyanate esters (II
) is an organic compound having two or more phosphoric acid ester groups and its prepolymer, and is a compound represented by the general formula (3). Specifically, examples are 1 and 3.
The case is 1,4-dicyanatobenzene, 4゜4-dicyanatobiphenyl, bis(4-cyanatophenyl) meta/, 2,2-bis(4-cyanatophenyl)propane, bis(4- Typical examples include cyanatophenyl) sulfone.

The above-mentioned polyfunctional cyanate ester can be used in the form of a prepolymer with an amine in addition to the above-mentioned prepolymer. The following can be mentioned.

In the present invention, the [C] acid component is a pre-reacted product obtained by pre-reacting the polyfunctional maleimide (1) and the polyfunctional cyanate ester alone or without a catalyst or in the presence of a catalyst. , are appropriately selected and used depending on the purpose.

The resin composition of the present invention includes 5 to 30 M parts of the CB) component and 50 to 20 M parts of the [C] component per 100 parts by weight of the [a) component.
It is necessary to use it at a composition ratio of 0tt parts.

[B] If the amount of thermosetting polysulfo/resin containing an acid component is less than 5 parts by weight, optical impact resistance will not be exhibited and it will be impossible to satisfy the present invention, and if the amount is more than 30 parts by weight. The viscosity at room temperature is extremely high (and the workability is significantly reduced).

In addition, when the amount of the compound selected from the group consisting of polyfunctional maleimides (1), polyfunctional cyanate esters (II), and pre-reacted products thereof, which have the [C] acid component, is less than 50 parts by weight. , it is opaque in terms of heat resistance and water resistance, and conversely, if it exceeds 20 oxt, the adhesiveness to the substrate is poor.

As an example of a preferred embodiment of the present invention, 100 parts by weight of epoxy resin, 1011 Lt parts of thermosetting polysulfo, and polyfunctional maleimide (1) and polyfunctional cyanate ester (n) are mixed in a weight ratio of 1/1. A composition using 100 parts by weight of a pre-reacted product pre-reacted with = O, ] ~ 0.8 can be cited, and according to this embodiment, the composition has better heat resistance, water resistance and resistance than conventional epoxy resin cured products. A final resin product with significantly improved impact properties can be obtained.

Various catalysts can be added to the resin composition of the present invention for the purpose of imparting desired properties to the cured resin product or adjusting the thermosetting properties of the resin. In addition to latent curing catalysts such as boron trifluoride amine complexes, triethylenediamine, 1,8-diazabicyclo(5+4
,0) tertiary amines such as /decene, N,N-dimethylbenzylamine, N-methylmolpoly/, and tri-n-butylamine, and organic compounds such as dicumyl peroxide, benzoyl peroxide, and t-butyl hydroperoxide. Examples include organic acid metal salts such as peroxide, zinc octylate, tin octylate, zinc naphthenate, and cobalt naphthi/acid. The catalyst to be used and the amount to be used may be determined depending on the purpose, but from the viewpoint of stability of the resin composition, it is generally not more than 3% by weight or more than 0.01% by weight based on the total resin solid component. It is preferable to use

It is also possible to mix and use additives such as pigments, dyes, stabilizers, plasticizers, and asphalt in the epoxy resin composition of the present invention, if necessary.

Furthermore, in addition to the prepreg base material described below, fibrous or powdered reinforcing materials or fillers such as glass mat, paper, asbestos paper, mica flakes, etc. can also be included.

The epoxy resin composition of the present invention is heated to a temperature of 170 to 250°C.
It has moderate storage stability and work stability at room temperature, and the cured product has significantly improved heat resistance, water resistance, and impact resistance compared to conventional heat-resistant epoxy resin cured products. Because of this, it can be used as adhesives, cast products, molding materials, paints, and laminated materials. It is particularly suitable as an epoxy resin for prepregs. There are no particular limitations on the base material used as the prepreg, but inorganic fibers such as glass fiber, carbon fiber, poron fiber, silicon carbide fiber, and poly-p-
Yarn, tape, sheet, or knitted fabrics made of one or more of phenylephthalamide, poly-p-benzamide, and polyamide hydracite organic fibers can be mentioned. In order to manufacture prepreg, general prepreg manufacturing methods can be applied, such as direct impregnation using a hot melt method or film method, or direct impregnation using a lacquer method or impregnation after film formation. The prepreg impregnated with the epoxy resin composition of the present invention cures at 170°C to 250°C and has appropriate storage stability and work stability at room temperature, and the cured laminate has excellent heat resistance, water resistance, It can have excellent mechanical strength in addition to impact resistance.

〔Example〕

Hereinafter, the present invention will be explained in more detail using Examples.

Synthesis Example 1 Synthesis of thermosetting polysulfone A molecule with an OH group at its terminal! 22,000 VICTREX ]OOp
(trademark manufactured by ICI) 200 parts to 100 parts of cyclohexanone/menal ethyl keto/mixed solvent with an IT ratio of 90/10
Add 10 parts of epichlorohydrin to this and add a 10% solution of sodium hydroxide while stirring at 45°C.
80 parts were added little by little and reacted for 90 minutes.

After the reaction, the solvent and excess shrimp chlorhydride were distilled off under reduced pressure, and the resulting viscous product was dissolved in toluene and washed with hot water until it became neutral, and then the solvent was distilled off. Then, it was dried at 110°C in a hot air dryer. The formation of epoxy groups in the obtained solid material was confirmed by an infrared spectrophotometer.

Examples 1 to 3, Comparative Examples 1 to 3 Epoxy tJ24 Ebot) 100 parts of YH-434 (trademark manufactured by Tobu Kasei Co., Ltd.), 30 parts of 4,4'-diaminodiphenylsulfone, and the thermosetting obtained in Synthesis Example 1 Add polysulfone resin in the proportions shown in Table 1, dissolve it in 7100 parts of methyl ethyl keto to make a homogeneous solution, and add bis(4-maleimidophenyl)methane and 2,2-bis
A prepolymer prepared by preliminarily reacting 4-cyanatophenyl)propane at 130°C for 4 hours in the proportion shown in mlH and 0.2 part of dicumyl peroxide were added, and the mixture was stirred at 50°C for 1 hour to form a homogeneous methyl ethyl ketone solution. did. Next, the methyl ethyl ketone was removed from the solvent, and the resulting resin was sandwiched between glass plates to a predetermined thickness, cured at 180°C for 2 hours, and further subjected to Boss)=F nearing at 240°C for 4 hours.

In addition, the carbon fiber Pyrophil AS (trademark manufactured by Mitsubishi Rayon Co., Ltd.) K was impregnated using the above-mentioned methyl ethyl keto/solution, and a prepreg was obtained by the drum winder method (+45/
90/-4510/+45/90) IIK laminated, 18
It was cured at 0°C for 2 hours and then at 240°C for 4 hours to obtain a composite material with a fiber volume content of 65.0%. Various tests were conducted on resins and composite materials, and the results are shown in Table 1.

In Table 1, the glass transition point (TP) is Rheometrlc.
The impact resistance of the composite material was measured by Ef
Manufactured by fect Technology Inc., Dynat
Up Model 8000 was used for P engineering (1ncipient 1oo) under the impact energy condition of 60.6 J.
d: klil), PF (fiber frac)
turefood (klil) and absorbed energy (Eo:J) were measured. As a result, Examples 1 to 3
It was confirmed that the sample had superior performance in heat resistance, water resistance, mechanical strength, and impact resistance as compared to the comparative example, and had an excellent balance of the above-mentioned properties.

〔Effect of the invention〕

The epoxy resin composition of the present invention has high heat resistance, excellent impact resistance and water resistance, and exhibits excellent performance for composite materials with carbon fibers and the like.

Procedural amendment (voluntary) September 29, 1980 Mr. Manabu Shiga, Commissioner of the Patent Office 1.Display of the incident Patent Application No. 1983-108043 2. Name of a Ming Dynasty epoxy resin composition 3. Person who makes corrections Relationship to the incident: Patent applicant 2-3-19 Kyobashi, Chuo-ku, Tokyo (603) Mitsubishi Rayon Co., Ltd. President and Director Akio Kawasaki 4. Deputy manager 3-19 Kyobashi Ko-chome, Chuo-ku, Tokyo Spontaneous / Par \, hydrazide”

Claims (1)

[Scope of Claims] 1. [A] Epoxy resin CB) Polysulfone resin [C] Polyfunctional maleimides (1), polyfunctional shea/acid esters (II), and the above (1) and ([1) A thermosetting product obtained by mixing or pre-reacting with at least one pre-reactant selected from the group consisting of pre-reactants, containing a repeating unit group represented by epoxy at °C, and reacting with epichlorohydrin at an 0H7Cl ratio of less than 1.0. The epoxy resin composition according to claim 1, which is a polysulfone resin. 3. The epoxy resin composition according to claim 1, wherein the composition ratio is 5 to 3 parts by weight of [B] and 0 to 200 parts by weight of [C] per 10 oxt parts of CAI.