JPS5829322B2 - Flame-retardant molding resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition comprising a halogenated polyalkenylphenol, an epoxy resin, and an additive, and a cyclic phosphate ester and/or thiophosphite added thereto. The present invention provides a molded layer epoxy resin composition with excellent flame retardancy and heat resistance.

Halogenated polyalkenylphenol, which is similar to halogenated polyvinylphenol, is a very unique reactive and polymeric flame retardant, and when combined with epoxy resin, it has excellent thermosetting properties that provide both flame retardancy and heat resistance. It is known that a synthetic resin composition can be obtained (Japanese Patent Application Laid-open No.
3599), laminates, adhesives, cast products, molded products, etc., and various proposals have been made.

The present inventors also paid attention to the characteristics of the composition obtained by blending a halogenated polyalkenylphenol and an epoxy resin, and in order to obtain a molding layer epoxy resin composition desired in the electrical and electronic industry fields, We have conducted various studies on this product and found that when halogenated polyalkenylphenol and epoxy resin are blended and heated to melt in the presence of an appropriate curing accelerator, the curing reaction progresses relatively rapidly and gelation occurs in a short period of time. There is a phenomenon that occurs.

In order to obtain a molding material from the above-mentioned blend of halogenated polyalkenylphenol and epoxy resin, the resin, filler, curing accelerator, etc. are heated and melted at about 150 to 170°C, and if necessary, It is necessary to undergo a step of semi-curing (B-stage) at a temperature of about 160° C., and excessive progress of the curing reaction must be suppressed until these steps are completed.

In order to solve the above-mentioned problems, the present inventors conducted a more detailed study and found that a composition consisting of a halogenated polyalkenylphenol, an epoxy resin, a filler, etc. It was discovered that adding thiophosphite esters can extend the gelation time, and by performing the heat-melting process and semi-curing process under normal conditions, it becomes possible to easily produce molding materials. The present invention was completed by determining the following.

Therefore, the main gist of the present invention is to provide a flame-retardant molding resin composition comprising a composition comprising a halogenated polyalkenylphenol, an epoxy resin, and a filler, and a cyclic phosphate ester and/or a thiophosphite. Regarding.

The effect of prolonging gelation time by phosphite esters found by the present inventors cannot be obtained by using similar compounds such as phosphate esters and phosphines. This is a unique effect found only in phosphite esters, which was discovered for the first time through detailed research by the inventors (see the experimental examples and comparative experimental examples in Example 1).

The halogenated polyalkenylphenol used in the composition of the present invention can have a wide range of polymerization degrees, from dimers to trimers to hundreds of polymers, but workability,
In view of the physical properties of the resulting molded product, a polymer having a degree of polymerization of approximately 10-150 mers is preferable.

The unit monomer constituting the polymer may be o-, m-, or p-alkenylphenol halides or a mixture thereof, and the polymer may contain one or more halogens. It may be.

Further, other synthetic resins such as polyalkenylphenol may be mixed with the halogenated polyalkenylphenol.

Such halogenated polyalkenylphenol may be produced by any method, but it can usually be prepared by the following method.

First, alkenylphenol is polymerized by thermal polymerization, ionic polymerization, radical polymerization, etc. to produce polyalkenylphenol, or acyloxyalkenylbenzene such as acyloxystyrene or alkoxyalkenylbenzene such as alkoxystyrene is polymerized and then the polymerization is performed. Polyalkenylphenols are produced by hydrolyzing substances.

The alkenylphenol hexamer used in this case is a monohydric phenol having a linear alkenyl group having 2 or more carbon atoms or a branched alkenyl group having 3 or more carbon atoms.

Among these, alkenylphenols having an alkenyl group having 2 to 4 carbon atoms are preferred.

For example, vinylphenol (hydroxystyrene),
n-propenylphenol, isopropenylphenol, n-butenylphenol, sec-butenylphenol,
Tertiary butenylphenol and the like.

In particular, a monohydric phenol having an alkenyl group having 2 to 3 carbon atoms is desirable.

Furthermore, as the polyalkenylphenol of the present invention, an alkenylphenol copolymer obtained by copolymerizing alkenylphenol with another polymerizable heptamer can be similarly used.

Examples of other polymerizable polymers include styrene, α-methylstyrene, chlorostyrene, bromostyrene, acrylonitrile, hinyl chloride, acrylic esters, methacrylic esters, maleic anhydride, and vinyl esters of various organic acids. be.

Furthermore, resol resins obtained by reacting these polyalkenylphenols with an excess of formaldehyde in the presence of a basic catalyst, novolak resins obtained by reacting these polyalkenylphenols with a slight excess of formaldehyde in the presence of an acidic catalyst, Alternatively, polyalkenylphenol derivatives such as partially hydrogenated products of these polyalkenylphenols can also be used.

The polyalkenylphenol is then treated with a common halogenating agent such as molecular chlorine, bromine, iodine, etc. or N-bromosuccinimide, chloramine T, etc. to obtain the polyalkenylphenol.

For example, a halogenated polymer having a desired substitution rate can be easily produced by uniformly dissolving polyalkenylphenol in methanol and then adding molecular bromine or blowing molecular chlorine in gaseous form.

By appropriately selecting reaction conditions and depending on the type of halogen used, the halogen content can be introduced in the range of about 20 to 70 parts by weight.

For formulation with epoxy resins, the halogen content is usually 30
~60% by weight of a brominated polyalkenylphenol or 30% of the bromine of this brominated polyalkenylphenol
The most commonly used one is one in which moles φ or less are substituted with chlorine.

As the epoxy resin to be blended with the halogenated polyalkenylphenol, any commonly used epoxy resin mainly consisting of a compound having at least two epoxy groups in one molecule can be used.

For example, bisphenol-based epoxy resins, novolac-based epoxy resins, polyphenol-based epoxy resins, polyhydroxybenzene-based epoxy resins, polyglycol-based epoxy resins, aromatic and aliphatic carboxylic acid-based epoxy resins, alicyclic epoxy resins, and nitrogen-containing epoxy resins. A resin, a metal-containing epoxy resin, or a halogen-substituted product of the above epoxy resin can be used.

The blending ratio of halogenated polyalkenylphenol and epoxy resin may be adjusted as appropriate depending on the characteristics of the molded product to be obtained, working conditions, etc. It is preferable that the ratio to the number of hydroxyl groups is in the range of 20/1 to 0.1/1, preferably 10/1 to 0.2/1.

Curing of halogenated polyalkenylphenol and epoxy resin progresses by heating to 140°C or higher, but
In order to shorten the curing time and obtain a molded article with good physical properties, it is desirable to use a commonly used curing accelerator.

Examples of these curing accelerators include tertiary amines such as dimethylaminobenzaldehyde, dimethylbenzylamine, and triethanolamine, polyamines such as diethylenetriamine, other urea, dicyandiamide, dimethylformamide, imidazoles, boron trifluoride,
Examples include amine complexes.

Examples of additives used in the molding resin assembly of the present invention include various fillers, mold release agents, pigments, and other modifying agents.

As the filler, various materials such as silica, alumina, quartz, calcium carbonate, calcium silicate, barium sulfate, glass fiber, carbon fiber, etc. can be used.

The blending ratio of these fillers is 10 to 1.0 with respect to the total amount of halogenated polyalkenylphenol and epoxy resin.
00phr.

Preferably, a range of 20 to 800 phr is appropriate.

Furthermore, compounds such as antimony and molybdenum, which are inorganic flame retardants, may be added to the resin composition of the present invention.

As the phosphite or thiophosphite used in the present invention, any of triesters, diesters and monoesters can be used.

Among these, triesters are preferred from the viewpoint of gelling prevention effect and compatibility with resin.

Among them, triphenyl phosphite, tritolyl phosphite, trinonylphenyl phosphite, tri-β
- Naphthyl phosphite, tricyclohexyl phosphite, tritetrahydrofurfuryl phosphite, diphenyldecyl phosphite, diphenylisooctyl phosphite, phenyldidecyl phosphite, nonylphenyl di-n-propyl phosphite, tribenzyl phosphite, tri- Decyl phosphite, trioctyl phosphite, tridecyl phosphite, triotadecyl phosphite, tri-2-ethylhexyl phosphite, trioleylphosphite, triallylphosphite, triphenylthiophosphite, tribenzylthiophosphite, Tridodecyl thiophosphite, trioctyl thiophosphite and the like are preferred.

The amount of these phosphite or thiophosphite added is preferably in the range of 0.05 to 10 phr based on the total amount of halogenated polyalkenylphenol and epoxy resin.

The method for preparing a molding phase from each fraction as described above is the same as the method for preparing ordinary epoxy resin molding materials.

That is, an epoxy resin is mixed with a halogenated polyalkenylphenol (and a mixture of polyalkenylphenol as necessary) to which the required amount of phosphite and/or thiophosphite has been added in advance,
After heating to completely dissolve, a curing accelerator is added and mixed.

Subsequently, a filler and a mold release agent are added, and the mixture is melted and kneaded under heating, and if necessary, it is crushed, heated, B-staged, cooled and solidified, and then crushed to form a phase for molding.

A molded article obtained from the resin composition of the present invention can be easily obtained by any of compression molding, injection molding, and transfer molding.

The molded product thus obtained has a bromine content of 15% or more and U
Excellent flame retardancy of L94 method V-O, heat distortion temperature 200℃
In addition to exhibiting the above-mentioned excellent heat resistance, it also has excellent dimensional stability with a molding shrinkage rate of about 1/10 compared to conventional epoxy resin molded products, and has superior electrical properties and mechanical strength compared to conventional molded products. Because it has excellent performance that surpasses that of conventional products, it is useful as a material for electronic and electrical equipment and as a variety of structural materials.

Example 1 Polyparavinylphenol (Maruzen Resin M manufactured by Maruzen Sekiyu KK, weight average molecular weight 4,000, hydroxyl equivalent weight 120)
), brominated polyparavinylphenol obtained by brominating this (Maruzen Resin MBJ manufactured by Maruzen Sekiyu KK)
Brome-containing i5 (IQ poly, hydroxyl equivalent 240), epoxy resin (Epicote 828 Bisphenol-based manufactured by Nigel Chemical Co., Ltd., epoxy equivalent 175-210), curing accelerator *-(BF3.piperidine) and increasing gelation time Table 1 shows the results of mixing various phosphorus-based compounds in the proportions shown in Table 1, heating the mixture to 140°C, and measuring the time required for gelation.

Example 2 The same brominated polyparavinylphenol, polyparavinylphenol, epoxy resin, curing accelerator,
Triphenylphosphite and Hoechstwax E (manufactured by Hoechst) as a mold release agent, and silica (manufactured by Hoechst) as a filler.
Fuzurex RD-8) was used in the proportions shown in Table 2.

120% polyparavinylphenol and Epicote 828
After mixing at ~130°C, brominated polyparavinylphenol with added triphenylphosphite was added and heated to 165-170°C to dissolve.

When the temperature dropped to 140°C, a curing accelerator, followed by silica and a mold release agent were mixed and kneaded at a temperature of 100 to 110°C for 5 minutes.

The resulting mixture was cooled and solidified, then ground and heated in an oven for 14 hours.
The mixture was heated and held at 0° C. for 10 minutes to B-stage, and then ground into a compound.

Subsequently, a predetermined amount of the compound was filled into a mold heated to 160°C, compression molded at 160°C and 50 kg/lst for 5 minutes, and then extracted from the mold and subjected to a predetermined post-curing treatment to obtain a molded article.

The heat distortion temperature and combustion test results of the molded product are shown below.
Shown in 2.

Further, the test results of the general physical properties and chemical resistance of the molded article obtained in Experimental Example 6 are shown in Table 3.

The chemical resistance was determined by a 7-day immersion test on a sample with a size of 1 mm x 507 x π x 507 n11 L.

Example 3 A predetermined amount of the compound obtained in Example 2 was preheated to 80°C, mold clamping pressure was 20 Ton1 injection pressure was 50 kg/cf!
Transfer molding was performed at a mold temperature of 180° C. and a curing time of 1 minute, followed by post-curing at 170° C. for 2 hours.

The obtained molded product had no sink marks or "voids" and had excellent surface smoothness, and also had very good secondary processability such as cutting.

Claims (1)

[Claims] 1. A composition comprising a halogenated polyalkenylphenol, an epoxy resin, and an additive, and a ring phosphate and/or
Or a flame-retardant molding resin composition containing a thiophosphite. 2 The ratio of the number of epoxy groups in the epoxy resin/the number of hydroxyl groups in the halogenated polyalkenylphenol is 20/1.
The flame-retardant molding resin composition according to claim 1, which has a molecular weight of 0.1/1. 3 ring phosphate ester and thiosulfite ester,
The flame-retardant molding resin composition according to claim 1 or 2, which contains 0.05 to 10 phr based on the total amount of halogenated polyalkenylphenol and epoxy resin.