JPS6218460A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having a high curing rate and excellent heat resistance, flame retardance, moldability and mechanical strength and useful as a molding material, an adhesive, etc., consisting mainly of a polystyrylpyridine resin and an epoxy resin. CONSTITUTION:A pyridine derivative contg. at least two methyl groups at 2- and 4- or 2- and 6-positions and an arom. dialdehyde are polycondensated to obtain a polystyrylpyridine resin (A) of the formula. 10-99wt% component A, 90-1wt% epoxy resin (B) contg. a curing agent (e.g. ethylenediamine) and a curing accelerator (e.g. chlorophenyl urea), 0-70wt% other resin (C) (e.g. phenolic resin) and 5-98wt% filler (D) (e.g. glass fiber) are kneaded together.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention generally relates to polystyrylpyridine resin (hereinafter referred to as PSP).
The polycondensation product of at least one aromatic dualdehyde derivative, called a resin) and at least a pyridine derivative containing at least two reactive methylated substituents, and an epoxy The present invention relates to a resin composition that can be used as a molding material, adhesive, etc.

(Prior Art and its Problems) In recent years, the aerospace industry has made remarkable progress, and the need for lightweight materials that can withstand high temperatures has also increased in the electronics industry, automobile industry, and the like.

That is, in the aerospace industry, there is a desire to reduce fuel costs and increase payload, and lightweight, heat-resistant materials are required for parts that are exposed to high temperatures due to air friction at high speeds or near power.

Furthermore, in the electronics industry, there is a demand for the development of heat-resistant insulating materials due to the increased density of ICs. Apart from these, there is a desire to develop materials that can withstand high temperatures and emit less smoke when burned, in order to help ensure the safety and evacuation of passengers in the event of flames occurring in aircraft or high-speed vehicles. PSP resin is a material that meets these requirements, and is expected to develop in the future, but the resin requires a curing reaction at a high temperature of 200°C or higher for several hours, resulting in poor productivity. has become a big problem.

(Means for Solving the Problems) The present inventors investigated the above problems and found that by adding an epoxy resin to PSP resin, the curing reaction becomes faster, and the heat resistance and flame retardance are excellent. This finding led to the present invention. Namely, the present invention provides a resin composition comprising a PSP resin and an epoxy resin, and optionally other resins and fillers.

PSP resin (polystyrylpyrinone resin), which is an essential component in the present invention, has at least two methyl groups of 2.4
Alternatively, it can be obtained by polycondensation reaction of one or more virison derivatives contained at the 2.6 position and one or more aromatic dialdehydes, preferably terephthalaldehyde. Such resins are described, for example, in French patents 2261296 and 226129.
It can be made using the method described in No. 7.

It is desirable that the 4-oxy resin used in the present invention has at least two epoxy groups in one molecule, and is usually a commercially available epoxy resin, such as one manufactured by Dainippon Ink and Chemicals Co., Ltd. These include those sold under the Epicron trademark. More preferred epoxy resins have excellent heat resistance and flame retardancy, and include, for example, brominated epoxy resins and phenolic epoxy resins.

The above-mentioned epoxy resin is usually used in combination with a curing agent, and the curing agent used together is preferably an amine compound having at least two hydrogen atoms in the molecule, such as ethylenediamine, triethylene, etc. Aromatic and aliphatic amines such as soamine, diethylenetriamine, tetramethylenediamine, duminodibuenyl sulfone, cyaminodiphenolmethane, nocyandiamide, dalicidylamine, hexamethylenetetramine, polyamide oligomer, hydantoins, incyanurates Various mono- or polyamines can be used, such as.

In addition, acid anhydrides can also be used as curing agents, and acid anhydrides have one or more acid anhydride groups in one molecule,
Examples include maleic anhydride, methylnadic anhydride, tetrahydrophthalic anhydride, trimetic anhydride, pyromellitic dianhydride, and various other aromatic and alicyclic acid anhydrides. Furthermore, a curing accelerator for epoxy resins can be added to the resin composition of the present invention if necessary, and examples of curing accelerators commonly used for epoxy resins include chlorophenylated ureas, boron trifluoride derivatives, and hydantoin derivatives. What is known as a curing accelerator can be used.

Other resins that can be used in the present invention include PSP resins and blend resins, and any resin that does not impair the purpose of the present invention may be used, such as phenol resins, melamine resins, urea resins, and furan resins.

Thermosetting resins such as xylene resins and thermosetting polyimide resins; polyarylene resins, polyarylene sulfide resins, polyarylene ketone resins, polyarylene ether resins, polycargenate resins, polyvinyl chloride resins,
Polysulfone resin, polyimide resin, f! Liamideimide resin, polyamide resin, polyurethane resin, polyester resin.

Examples include thermoplastic resins such as fluororesins. Of course, other resins are appropriately selected depending on the intended use of the composition of the present invention.

Examples of phenolic resins, melamine resins, xylene resins, urea resins, and furan resins (abbreviated as phenolic resins) that can be used in the present invention include phenol, cresol, alkylphenol, alkylcresol, melamine, urea, and furfural.

It is a product obtained by condensing furfuryl alcohol or the like with an aldehyde such as formalin or glyoxol in the presence of an acid or alkali catalyst, such as Plyophen and Percam manufactured by Dainippon Ink and Chemicals.

Resins commercially available under trademarks such as FAWANDREZ can be used.

Polyimide resins that can be used in the present invention include bismaleimide and its derivatives, such as polyamino bismaleimide manufactured by Rhône f-Rough, France, which is generally known as kelimide or quinerno, and BT resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.).
Thermosetting polyimide resins such as bismaleimide-triazine resins are preferred, but other polyimide resins can also be used.

Among the other resins mentioned above, the processing temperature of PSP resin, e.g. 2
Those that melt at about 00°C are preferred, and specifically phenolic resins and thermosetting polyimide resins are preferred.

Incidentally, when a phenolic resin and a thermosetting polyimide resin are used in combination, not only excellent heat resistance and flame retardance can be obtained, but also an improvement effect of low smoke generation can be expected.

The blending ratio of PSP resin and epoxy resin in the composition of the present invention is not particularly limited, but considering the moldability, heat resistance, etc. of the composition, it is preferable to use PSP resin in the total of PSP resin and epoxy resin. 10 ~ PSP for sure! The content of A fat is 60 to 90% by weight and 1% by weight and epoxy resin is 40 to 0% by weight.

Further, the appropriate blending ratio of other resins is 0 to 70 times the total of PSP resin, Nikin resin and other resins.

Fillers can be added to the compositions of the invention. Such fillers include glass fiber, carbon fiber, metal fiber, and aramid fiber. Ceramic fiber.

Potassium titanate, asbestos, silicon carbide, ceramic, silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, nozoirophyllite.

bentonite, sericite, zeolite, mica.

Mica, nephelinsinite, talc, atarno4gite, wollastonite, PMF, ferrite.

Calcium silicate, calcium carbonate, magnesium carbonate,
Dolomite, ammonium trioxide, zinc oxide.

Titanium oxide, magnesium oxide. iron oxide. Molybdenum disulfide, graphite 1 gypsum, glass beads, glass powder, glass balloon, quartz. Quartz d5s.

Examples include fluororesin and 2-carbon resin, and fibrous fillers are preferred. The shape of the fibrous filler is long fiber,
Short fibers, 9 knitted woven fabrics, sheets, mats.

Beno J? It can be used in the form of -. The amount of DO added to the filler in the composition is suitably 5 to 98% by weight, preferably 20 to 90% by weight.

Since the composition of the present invention can shorten the curing time, it is possible to reduce the curing time. It is preferable to use a curing agent and a curing accelerator for the resin in combination. The amount of the curing agent is 12 to 2.0% active hydrogen per mole of epoxy groups in the epoxy resin. The amount of the curing accelerator is 0 mole, and the appropriate amount of the curing accelerator is 0 to 10% by weight of the total resin component.

The resin composition of the present invention can be used as a partially cured molding material by impregnating the resin into a fibrillar filler, heating if necessary to remove the solvent, and the material can be roughly divided into 1.
There are two types: those using short fibers of 0 cIn or less and those using long fibers of 10 cPn or more.

Products using short fibers are injection molding materials that are made into pellets after mixing the fibers and resin to a semi-cured state.
Materials for injection molding and hot press molding in the form of short fibers, which are semi-cured by coating resin on the surface of fibers, and so-called sheet molding materials, which are made by mixing fibers and resin and forming a semi-cured sheet into a semi-cured state. Luding Con/4' Wound, so-called bulk molding con made by mixing fibers and resin and making it into a block and semi-hardened state) J? flint',
Examples include a molding material in which short mi is previously formed into a sheet, mat, or paper shape, and this is impregnated with a resin component to bring it into a semi-cured state.

In addition, as for products using long fibers, there are fabrics woven with long fibers in advance,
Knitted fabrics, sheets, mats, beano mats, etc. are made in advance, and then impregnated with resin and made into a semi-cured state, Silipreg and long fibers (tow) themselves or the long fibers are aligned in a certain direction, impregnated with resin and semi-cured. Mention may be made of so-called towgrigs and unidirectional prepregs in a cured state.

These molding materials are used depending on the shape, required performance, required number, etc. of the final molded product, and are molded by various methods such as injection molding, hot press molding, autoclave molding, and transfer molding.

Of course, the resin composition of the present invention can also be molded by the so-called hand lay-up method by adding a strong acid such as phosphoric acid, sulfuric acid, or hydrochloric acid as a catalyst; Good.

When a fibrous filler is used in conjunction with the present invention, various solvents can be used as necessary to reduce the viscosity and facilitate impregnation when impregnating the filler with resin. Examples of such solvents include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, furonol, butanol; esters and nitrogen such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cellosolves, and ethyl ether. Chills;
O aromatics such as benzene, toluene, xylene? Class II: 7-logonized hydrocarbons such as chloroform, carbon tetrachloride, methylene, chloride, trichloride, etc. High boiling point solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolid, etc. can be used. .

When adding these solvents to lower the viscosity of the resin and impregnating it into fibers, the solvent is removed by heating and at the same time the resin is
It can be staged, but the amount of residual solvent at that time is 10 weight-t.
It is desirable to have a bite of less than 100 lbs., and more preferably less than 2 weights.

The composition of the present invention can be cured usually at 100 to 250°C, preferably at 150 to 250°C.

(Effects of the Invention) The composition of the present invention has excellent heat curability, moldability, heat resistance, flame retardancy, mechanical strength, etc., and is used in various applications, such as equipment surrounding high-speed rotating parts (around engines, Molding of electrical/electronic equipment (IC boards, microwave oven parts, etc.), aerospace equipment (rockets, missiles, outer walls of artificial satellites, interior parts of aircraft, vehicles, hovercraft, etc.), etc. It can be used for materials, heat-resistant adhesives, etc.

(Example) Next, the present invention will be further explained with reference to Examples and Reference Examples. Note that parts and parts in the examples are based on weight.

[Example 1] (Creation of prepreg) PSP 6022M (PSP resin, resin content 75%, 5
Add 23.3 parts of Ebicuron N-740-80M (resin content: 80 parts, Dainippon Ink & Chemicals Co., Ltd.) and 6.4 parts of diaminodiphenylsulfone (1st class reagent) to 33 parts of NPE Co., Ltd. as an epoxy resin. In addition, it was diluted with acetone to prepare a solution with a solid content of 40%. The content of PSP resin in the solid content of this solution was 80%.

Carbon fiber trading card cloth 6343 (fabric weight 200.9 parts m", Toshiku Co., Ltd. Tan) was impregnated with this solution and heated at 130°C.
B-stage was obtained by drying for 6 minutes to obtain a woven prepreg. This prepreg was sufficiently flexible and in good condition with little surface tackiness. Moreover, the prepreg has 3
With a weight of 0.9 parts m2, the gluing time is 10 at 200°C.
It was a minute. The residual amount of volatile matter was 1.5%.

[Example 2] 15 plies of prepreg from Example 1 were heated at 200°C and 50 #
Hot press molding was carried out under a pressure of /, 2, followed by demolding in 30 minutes to obtain a laminate. Thereafter, it was cured at 250°C for 3 hours. The obtained laminate has a fiber content of 68, JIS
Its physical properties were measured by the K-7203 method and the short beam method.

At room temperature, bending strength is 53 kg/ltm. Flexural modulus is 5.
200 to 2, interlaminar shear strength (ILSS) 3.2 to 2, bending strength at 250°C 45 kg/m", flexural modulus to 5000 to 9 parts m", ILSS 3.0 to 2.
It was 2.

The laminate of this example had good heat resistance and strength retention.

[Example 3] PSP 6022M 133 parts, Epicron N 74
0-80M 11.7 parts, diaminodiphenylsulfone 3
．． 2 parts.

0.5 part of chlorophenylated urea and 20.8 parts of Pryophen 5900 (resin content: 60%, Dainippon Ink & Chemicals Co., Ltd.) as a phenol resin were added, and the solid content was further reduced to 40% with acetone. Using the solution, a prepreg was obtained in the same manner as in Example 1. This prepreg was molded in the same manner as in Example 2, and its physical properties were measured.

At room temperature, bending strength is 52y7m and elastic modulus is 5500k.
i? /1m"ILSS 3.3kl?/mx" f
h'), 250℃ thermal bending strength 46! 9/1m2,
Same elastic modulus 4800 kI? /w2, ■r, ss 2. q
tg/2, indicating high strength retention at high temperatures.

[Example 4] PSP 6022M 133 parts, Epicron N740-
80M 11.7 parts, diaminodiphenylsulfone 3.2
and polyimide, 12.5 parts of Kelimide 601 (manufactured by Mitsui Petrochemical Industries, Ltd.) dissolved in cyaminoformamide in advance were mixed, and acetone was added to reduce the solid content to 4.
A prepreg was prepared by impregnating Trading Card Cloth 6343K with a 0% solution. This prepreg 107'll 20
Press molded at 0°C for 60 minutes under a pressure of 50 Yu/crn2,
After demolding, post-curing was performed at 250° C. for 5 hours, and the physical properties were measured.

At room temperature, the bending strength is 51 Y/■2 and the elastic modulus is 5000.
Ni 17/Parrot, II, SS 3.3 Yu/Kin 2, bending strength 46klil/Kaku 2 Modulus of elasticity 4700 Yu 7 m at 250°C.

ILSS 3. It was okg/throat 2.

[Example 5] In Example 1, the trading card cloth 6343 was replaced by Las Cross 5LS-213B (Asahi Fiberglass Co., Ltd.)
A prepreg was made using the same method as in Example 2, and the laminate was made into a laminate and its physical properties were measured.

Bending strength at room temperature: 50 yu/bit 2. Same elastic modulus 2500 to 9
7m"ILSS 3.2 Bending strength at 2,250℃ to the east is 43ky/w".

Same elastic modulus 2300y7m”, ILSS 2.8kg
/ Hidden 2 exhibited good high-temperature physical property retention.

[Example 6] Using the solution of Example 2 as the resin composition, and 6+a
After mixing long carbon fibers with short fibers (chopped fibers) and thinly dispersing them on silicon <-/#-,
It was dried at 0° C. for 10 minutes to obtain a sheet-like molding material of 50 strands of carbon fiber.

This was hot press molded for 60 minutes at 200°C + 50kg/Cyn'' pressure, and cured at 250°C for 5 hours to obtain a laminate.The physical properties of the laminate were a bending strength of 32kg at room temperature.
/m", the same elastic modulus is 3000 kg/gourd 2. At 250°C, the bending strength is 20 and 9/aaa", the same elastic modulus is 2100 kp.
/■2 showed good high temperature strength retention.

[Example 7] Ebicuron N-740 in 133 parts of PSP 6022M
-45 parts of 80M and dimethyldiphenylsulfone (X41
M) Dilute 6.4 parts with 770% acetone to reduce the solid content to 4
A 0% solution was made. Ps in the solid content of this solution
The content of P resin was 80%.

Next, a prepreg was produced in the same manner as in Example 1, and a laminate was further produced in the same manner as in Example 2 using this prepreg.

The obtained laminate has a bending strength of 5.3 kg/
w”, same elastic modulus 5200 to 9 parts wm”, ILSS
3.6 with 9 parts m2, bending strength 4 at 250℃
2 to 97m” Modulus of elasticity 4400 kg/m2. ILS
S 2.6 kll/lex""t' afc.

[Reference Example 1] Torekaku OS 6343 was impregnated with PSP 6022M and B-staged to produce a prepreg with a resin content of 40% 1i. 15 sheets of this prepreg Mn-C2001? :
Leave it on the press for 75 minutes without applying pressure.
Okg/cm” o ioo min under pressure, further 10 k
g/crr? The temperature was raised to 250℃ under the pressure of 12020℃.
A minute-press laminate was obtained. The laminate was further post-cured at 250° C. for 5 hours.

The result is a fiber-containing laminate of 67 mm, with a bending strength of 50 at room temperature of 97 m'', a flexural modulus of 5300 of 9 parts m'', and an ILSS of 3.0 klF/m'', 25
Physical properties at 0°C are bending strength 48 kp/a" 1 bending modulus 5600' and 9/2. ILSS 3.0 kli
'/m'.

Note that when the above Solepreg was molded under the same conditions as in Example 2, the resin flowed out during pressurization and heating, and a laminate could not be obtained.

Claims (1)

[Claims] A resin composition consisting of a polystyrylpyridine resin, an epoxy resin, and if necessary other resins and fillers.