JPS62201960A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent heat resistance, quick curability and moldability, consisting of a polystyrylpyridine resin and a bismaleimide resin. CONSTITUTION:A polystyrylpyridine resin (A) of formula I (wherein X is a group of formula II; Y is a group of formula III; R and R1 are each a hydrocarbon segment which may contain a hetero atom; A and A1 are each a steric transfer bonding group such as ether, sulfone, etc. and an atom or a group which forms a bridge between R and the arom. ring of the styrylpyridine ring; R2 is H, methyl or ethyl; k, l and m is an integer of 0 or greater and at least one thereof is always an integer larger than 0) is blended with a bismaleimide resin (B) having a viscosity of 100-50,000mm Pas, represented by the formula V (wherein R3 and R4 are each H or an alkyl; and U is a member selected from the group consisting of diphenylmethane, diphenyl ether, diphenyl sulfone, etc.) in a ratio of A to B of 1-9:9-1.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of application in aquaculture) The present invention relates to polystyrylpyridine resin (hereinafter referred to as psp
Represented as resin. ) and a bismaleimide resin, the present invention relates to a resin composition having excellent heat resistance, fast curing properties, and moldability.

(Prior art and its problems) PSP resin is made of aromatic dialdehyde such as tele-7taraldehyde and 2,6-lutidine, as described in French Patent No. 2261296 and No. 2378052
It is obtained by condensation with a collidine derivative substituted with at least two reactive methyl groups, such as 2°4.6-collidine, and is mainly used as a matrix for the production of prepregs. Prepreg molded products or molding compound molded products obtained from PSP resin have features such as excellent heat resistance, flame resistance, and low smoke emission. These features are extremely useful when applied to structural materials that require high-temperature/thermal properties, which are characteristic of the aerospace field. However, when molding PSP resin alone, regardless of autoclave molding, compression molding, etc., relatively high temperatures (
This requires curing at a temperature of usually 200° C. or higher) and a relatively long molding time (usually 6 to 8 hours). Such molding conditions are a major drawback, especially when used in applications that require high productivity.

On the other hand, based on the research results to date, we have found that mixing phenolic compounds such as resorcinol, novolac type, and resol type phenolic compounds with epoxy compounds typified by novolac phenol type epoxy resins is effective in accelerating the curing of PSP resin. It has been found that the molding time can be significantly shortened. However, improving the molding conditions by mixing with these resins had nine drawbacks, on the one hand, losing the heat resistance and other features inherent to PSP resin.

(Means for Solving All Problems) As a result of intensive research in order to solve the above-mentioned problems in molding PSP resin, the inventors of the present invention found that by mixing PSP resin and bismaleimide resin. As a result, it was discovered that pspmt resin can be cured at a relatively low temperature and in a short period of time without impairing its inherent features such as heat resistance, leading to the present invention.

That is, the present invention provides a resin composition comprising a polystyrylpyridine thread resin and a bismaleimide resin.

The psp resin used in the present invention has the following general formula (I)
k YI Zm ...... Indicates (I).

(Here, RlR, represents a segment that can contain a heteroatom made of the same or different hydrocarbons, AlA represents the same or different steric transfer bonding group such as an ether group or a sulfone group, and R and an atom tft forming a bridge between the aromatic ring of the styrylpyridine chain;
indicates fund, horse indicates hydrogen or methyl group, ethyl group,
k, 7. m indicates an integer that may be equal to 0. However, either one of A' and m is not O. )].

PSP resins can be produced, for example, according to French Patents No. 22,612.96 and No. 2,378,052. For example,
At least one aromatic dialdehyde derivative such as terephthalaldehyde and at least one pyridine conductor disubstituted by at least two reactive methyl groups such as 2,6-lutidine, 2,4,6-collidine, etc. Produced by polycondensation. Furthermore, PSP resins can be used in a variety of states at room temperature, from viscous liquids to powders, depending on the condensation rate K.

Furthermore, the bismaleimide resin used in the present invention is
General formula (II) [wherein R,, R, represents hydrogen or an alkyl group, U
represents gold such as diphenylmethane, diphenyl ether, diphenyl sulfone, etc. ] is used. Preferably it is a prepolymer. Examples of bismaleimide resins include commonly available resins such as "Kelimide" manufactured by Rosgoulan Co., Ltd. and "Konbuimide" manufactured by Boots Chikunonmie Co., Ltd., and bismaleimide represented by the general formula (n), amines, and hydrazides. It is obtained by the reaction with
Its viscosity is from 100 to 50,000 inPas. There is no particular restriction on the ratio of psp resin (AJ and bismaleimide JIIB+), but preferably (A)
: (Bl=1-9:9-1, more preferably 8-5
:5 to 2. It can be mixed as desired depending on the purpose and use.

In addition, radical initiators, aromatic diamino compounds, etc. have been added to the mixed system of PSP resin and bismaleimide resin as additives for the purpose of accelerating curing.
- Can be added in an amount of 10% by weight.

Examples of aromatic diamino compounds include 4,4'-diaminodiphenylsulfone (DDS) and 4,4'-diaminodiphenylpropane.

As the radical initiator, known ones can be used, such as benzoyl peroxide, 1,1-bis-1-peroxy-3,3,5-trimethylcyclohexane, t--
Examples include 19-ruboxybenzoate and azobisin butyronitrile.

Further, for the purpose of accelerating curing, an allyl compound may be added to the composition in an amount of 0 to 20% by weight, preferably 0 to 10% by weight. The allyl compound is a compound in which the ortho position and the rose position of a phenolic hydroxyl group-containing compound are substituted with W by an allyl group, and is a compound represented by the following general formula (Ill).

i'- [X means none, ■(, CH!, -C-, etc., R is H1e CH,, halogen atom, OR' (H, CH, CtHs)
Show money. ] Specific examples include 2-allylphenol, o
, o'-Diallyldiphenol A% o) o'
-Diallyldiphenol F1 eugenol, 4.4'-
Dihydroxy-3,6'-diallyldiphenyl, 2.
Examples include 2-bis(4-hydroxy-3,5-diallylphenyl)propane.

In addition, in order to improve brittleness, which is one of the drawbacks of PSP resin, other resins may be added in an amount of 0 to 50% by weight, preferably 0 to 20% by weight, based on the composition, within a range that does not significantly impair heat resistance.
% by weight can be added.

Other resins that can be used in the present invention include, for example, phenolic resins, melamine resins, urea resins, furan resins,
Thermosetting resins such as xylene resins and thermosetting polyimide resins; polyarylene resins, polyarylene sulfide resins, polyarylene ketone resins, polyarylene ether resins, polycarbonate resins, polyvinyl chloride resins,
Examples include thermoplastic resins such as polysulfone resin, polyimide resin, polyamideimide resin, polyamide resin, polyurethane resin, polyester resin, vinyl ester resin, and fluororesin.

Of course, other resins are appropriately selected depending on the intended use of the composition of the present invention.

Fillers can be added to the compositions of the invention. Such fillers include glass fiber and Charcoal Purple S! fiber, metal fiber, aramid fiber, ceramic fiber, potassium titanate, asbestos, silicon carbide, ceramic, silicon nitride,
Barium sulfate, calcium sulfate, Kaori/, clay, biophytite, bentonite, sericite, zeolite, mica, nephelinsinite, talc, atalbulgite, wollastonite, PMF, ferrite, calcium silicate, magnesium carbonate, dolomite,
Examples include ammonium trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass powder, fluoride, quartz, quartz glass, fluororesin powder, etc. fibrous fillers are preferred. The fibrous filler can be used in the form of long fibers, short fibers, woven fabric, II material, sheet, mat, paper, etc. The amount of filler added is 5 to 98 times, preferably 20 times, in the composition.
~90ii% is suitable.

The resin composition of the present invention can be used as a partially cured molding material by impregnating a fibrous filler with a resin component and removing the solvent by heating if necessary.
There are two types: one using short fibers of 0α or less and one using long fibers of 1ocn1 or more.

In the case of short fibers, the fibers are mixed with a resin and made into a semi-cured state, and then made into a pellet-shaped injection molding material. Materials for injection molding and hot press molding in the form of short strands, so-called sheet molding compounds that are made by mixing fibers and resins and making them into a sheet into a semi-hardened state.So-called sheet molding compounds that are made by mixing fibers and resins and making them into blocks. Examples include a so-called bulk molding compound in a semi-cured state, and a molding material in which short fibers are previously formed into a sheet, mat, or paper form and impregnated with a resin to become 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, vapor, etc. are made in advance, and prepreg and long fibers (tow) themselves or long zelkova fibers are aligned in a certain direction, impregnated with resin and semi-cured, and then impregnated with resin and semi-cured. Examples include so-called tow prepregs and unidirectional prepregs. Solvent method, hot melt method, etc. can be used to manufacture prepreg.

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, but if necessary, any of these molding methods may be used. You just have to choose.

When a fibrous filler is used in conjunction with the present invention, various targeting agents can be used as necessary to reduce viscosity and facilitate impregnation when impregnating the filler with resin. Examples of such solvents include ketones such as acetone and methyl ethylgtone; alcohols such as methanol, ethanol, globanol, butanol; esters and ethers such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, selonrupes, and ethyl ether; Aromatic solvents such as benzene, toluene, and quintylene; 710-genated hydrocarbons such as chloroform, carbon tetrachloride, methylene, chloride, and trichlene; Dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N
-High-boiling bath agents such as methylpyrrolidone can be used.

When adding these solvents to lower the viscosity of the resin and impregnate the fibers, the bath agent is removed by heating and at the same time the resin is
Although it can be staged, the amount of residual solvent at that time is preferably 10% by weight or less, and more preferably 2% by weight or less.

The composition of the present invention can be cured usually at 100 to 300°C, preferably at 120 to 250°C. When post-curing, it is preferable to do it at 180 to 270°C.

(Effects of the Invention) The composition of the present invention has excellent heat-curing properties, moldability, heat resistance, flame retardance, mechanical strength, etc., and can be used for various purposes, such as equipment surrounding high-speed rotating parts ( Around the engine, bearings,
($), electric/electronic equipment (IC boards, microwave oven parts, etc.), aviation/space equipment (rockets, missiles, etc.)
It can be used as a molding material for external walls of artificial satellites, aircraft, oil purifiers, interior parts of hovercraft, etc.), heat-resistant adhesives, coating compositions, paints, etc.

(Example) Next, the present invention will be described as an example, Reference 1+lleζ, and 14! i: Clarify.

Note that parts and percentages in the column are based on 1" amount.

Example 1 Bismaleimide resin and other additives were mixed with PSP resin in various proportions. The gelation time of these wet mixtures was measured in accordance with all JIS 6910 methods. Table 1 shows the results.
It was shown to.

Here, the psp resin is 5NPE company p (D "PsP 60
22MJ (resin content 75% MEK solution) was used as bismaleimide resin "Konbuimide 795J" manufactured by Boots Technosimi.
([fat content 99%)] All were used.

The gelation time of pure PSP resin is 1 at 200°C.
20 minutes, while that of combuimide 795 is 17 minutes.
50 ± 20 minutes at 5°C (DIN method), Table 1
More clearly, it was confirmed that mixing the bismaleimide resin with the PSP resin significantly shortened the curing time.

It is also clear that it is effective to add radical initiators, allyl compounds, etc.

Example row 2 According to the blending ratio of situation 2 in example 1, PSP6022M
.

Conguimide 795 was made into a solution with a resin solid content of 50% by weight using MEK. ≠181 type glass woven fabric was coated with a resin content of 45% by weight fc*, and B-staged at 110°C for 8 minutes to prepare a Jigly preg. The obtained prepreg gold was stacked on a press plate at 165℃ 2
It was left standing without applying pressure for 5 minutes. Next, at the same temperature for 5 minutes under pressure, and then at the same temperature for 25 k? After increasing the pressure to /i, the mixture was heated and pressurized for 25 minutes.

Then, the 'lkJ baseplate thus obtained was left to stand for 0 minutes under a pressure of ν/12 at 25°C at 180°C.
I did a time bot cure. Oj! The physical properties of the J-layer plate are shown in Table-2.

Table-2 Example 6 PSP6022M/Conbuimide 795,/Bismale f-mido S [Mitsui Toatsu Fine Wa Products]/o,
o'-diallylbisphenol A = 70/201515
(mt ratio) was mixed with MEK and DMF to make a solution containing 50% by weight of solid fat content. A resin content of 45:1lii% was applied onto the carbon fiber woven fabric (Besphi +3101 manufactured by Toho Rayon ■) in step 3, and 10% of the resin content was applied at 110°C.
The entire Sibripreg was prepared by B-staging for minutes. The obtained prepregs were stacked between press plates at 165° C. and allowed to stand for 30 minutes without being pressurized. Then at the same temperature 5
Pressure was applied for 10 minutes at +/i and for 20 minutes at 25°C. Continue to set the temperature to 180℃ and 25X? /c11?
The mixture was allowed to stand under pressure for 30 minutes. The obtained laminate was post-cured at 250°C for 5 hours. The physical properties of the laminate are shown in Table 3.

Table 3 Agent: Patent Attorney Katsutoshi Takahashi Procedural Amendment (Voluntary) May Z, 1986 Director General of the Patent Office Michibe Uga 1, Indication of the Case 1986 Patent Application No. 44220 2, Title of the Invention Resin Composition 3, Relationship with the Amendment Case Patent applicant: 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (2)
88) Dainippon Ink & Chemicals Co., Ltd. Representative Kawa
Kuni Mura Shigeru 4, agent telephone: Tokyo (03) 272-4511 (main representative) (
8876) Patent Attorney Katsutoshi Takahashi 5, Detailed explanation of the invention in the specification subject to amendment 6, Contents of amendment (1) Akira, i! Ill Homare, page 4, line 4 from the bottom [R
and styryl birinone chain J k lr R or R1 and styryl pyridine chain j.

(2) r 500.000wPam on page 6, line 8
J to F 50. Correct it as OOOmPam J.

(3) Corrected "r4.4'-diamino-nophenylnoropane" in lines 2 and 3 of page 7, "7r4.4'-diaminodiphenylmethane."

that's all

Claims (1)

[Claims] A resin composition comprising a polystyrylpyridine resin (A) and a bismaleimide resin (B).