JPH0320325A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To form a thermosetting epoxy resin phosphazene composition of excellent heat resistance without detriment to the excellent mechanical properties and workability inherent in an epoxy resin by mixing an epoxy resin with a specified cyclophosphazene derivative and a cure accelerator as essential components. CONSTITUTION:A thermosetting resin composition essentially consisting of an epoxy resin, a formylphenoxy-cyclophosphazene derivative of formula I (wherein (n) is 3 or 4; (p)+(q)=2; (p)>0; (q)>=0; (pn) is a positive integer; (qn) is 0 or a positive integer; and the formyl may be in any position ortho, meta or para to the benzene ring), and a cure accelerator. It is desirable to add 10-400 pts.wt. cyclophosphazene derivative to 100 pts.wt. epoxy resin and to use an onium compound or an amine as the cure accelerator.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel thermosetting resin composition with excellent heat resistance. The composition of the present invention is used as a laminated material, a casting material, a molding material, etc., and is useful for electrical/electronic parts and mechanical parts.

(Prior art) Epoxy resins not only have excellent electrical and mechanical properties, but also good compatibility and low liquefaction temperature, making them easy to work with. Widely used. However, as technology in these fields has recently become more sophisticated, there has been a need to improve the heat resistance of epoxy resins.
Various methods have been proposed.

For example, curing agents for epoxy resins with excellent heat resistance such as polyamino bismaleimide, maleimidophenol, and poly p-vinylphenol have been proposed, as well as improvements in epoxy resins themselves such as tetraglycidyldiaminodiphenylmethane and tetraglycidyl ether of penzophenone. have been studied, but nothing has been found that satisfies both the conventional workability and the required heat resistance.

On the other hand, cyclophosphazene derivatives, such as linear polyphosphazene derivatives obtained by ring-opening polymerization of hexachlorocyclotriphosphazene, are increasingly being used as industrial rubber materials due to their excellent heat resistance and chemical stability. However, there are only a few studies on the method of using cyclophosphacene derivatives in combination with other resins as a component of thermosetting resin compositions (although the use of cyclophosphacene derivatives to their full potential has not yet been done). Conventionally, it has been proposed to use diaminotetraorganocyclotriphosphacene as a curing agent for epoxy resins (Japanese Unexamined Patent Application Publication No. 61-1
No. 90522), Kakitata Hexa (4-aminophenoxy)
Research using cyclotriphosphazene, tri(4-aminophenoxy)triphenoxycyclotriphosphazene, or trichlorotridimethylaminocyclotriphosphazene as a curing agent for epoxy resins has been reported (Kobunshi Journal JVoA.45, l'lill,
851-856 (1988)), the heat resistance of the cured product is lower than that of conventional epoxy resin/diaminodiphenylsulfone in the case of epoxy resin compositions using cyclophosphazene derivatives as curing agents that have been proposed or research reported. It does not surpass that of the cured product of the system composition.

(Problems to be Solved by the Invention) An object of the present invention is to fully utilize the excellent heat resistance and flame resistance of phosphazene without impairing the excellent mechanical properties and workability of epoxy resin, An object of the present invention is to provide an epoxy resin/phosphazene-based thermosetting resin composition that provides a cured product with better heat resistance than the cured products of conventional epoxy resin/phosphacene-based compositions.

(Means for Solving the Problems) As a result of various studies on the characteristics of resin compositions containing epoxy resins and various cyclophosphazene derivatives, the present inventors found that certain cyclophosphazenes having a formylphenoxy group as cyclophosphazene derivatives. When using a high conductor, 70 to 25
The present invention was completed by discovering that a cured product with excellent heat resistance can be obtained by curing at 0C.

That is, the gist of the present invention is an epoxy resin, a cyclophosphazene derivative having a formylphenoxy group represented by the following general formula; (where n = 3 1t or 4, p + q = 2, p >
0, q≧0, pn is a positive integer, qn is Ot or a positive integer, and the formyl group may be located at any of the ortho, meta 1, or para positions of the benzene ring. ) or a mixture thereof and a curing accelerator as essential components.

To explain the present invention in more detail, the epoxy resin used in the present invention is not particularly limited, and all known epoxy resins can be used.

For example, bisphenol-type epoxy resin obtained by the reaction of bisphenol A and shrimp chlorohydrin, phenol novolac resin, novolak-type epoxy resin obtained by the reaction of cresol nopolak resin and shrimp chlorohydrin, polyvalent resins such as resorcinol or hydroquinone, etc. Polyhydroxybenzene type epoxy resin obtained by the reaction of phenolic resin and shrimp chlorohydrin, nitrogen-containing epoxy resin obtained by the reaction of aromatic amine such as toluidine or aniline with shrimp chlorohydrin, cyclohexene, vinylcyclohexene, cycloben. Alicyclic epoxy resins starting from tadiene, dicyclopentadiene, etc., butanediol, hexanediol, glycerin, } IJ) tyrolpropane,
Gee such as pentaerythritol! or polyol di-1 or polyglycidyl ethers, silicon-containing epoxy resin obtained by reacting epoxy resin with silanol,
Examples include epoxy resins having nitrogen-containing heterocycles obtained from incyanuric acid. These epoxy resins may be used alone or as a mixture of two or more.

1. The phosphazene derivative used in the present invention is a cyclophosphazene having a formyl 7-enoxy group represented by the following general formula (in the formula, n, p, q and the substitution position of the formyl group are the same as above). Sen derivatives, among which are hexa(formylphenoxy)cyclotriphosphazene, octa(formylphenoxy)cyclotetraphosphazene, formylphenoxyphenoxycyclotriphosphazene or formylphenoxyphenoxycyclotetraphosphazene. These compounds include hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene and hydroxybenzaldehyde 1
Alternatively, it can be obtained by reacting a mixture of hydroxybenzaldehyde and phenol. The hydroxybenzaldehyde may be used either as O- or m-p, or as a mixture.

In the above general formula, p and q are formyl 7 bonded to one phosphorus atom of the cyclophosphacene molecule.
The average number of enoxy and phenoxy groups! ),
This is why pn is defined as a positive integer and qn is defined as 0 or a positive integer. In other words, the substituents bonded to the three or four phosphorus atoms in the cyclophosphazene molecule can be selected independently.

The introduction ratio of the formylphenoxy group and the 7-phenoxy group can be freely controlled by the mixing ratio of hydroxypenzaldehyde and phenol used in preparing the phosphazene derivative used in the present invention. As the rate of introduction of phenoxy groups increases, the melting point of the phosphazene derivative decreases, which widens the range of options for formulation and preparation conditions in blending resin compositions.

For example, the introduction rate of p-formylphenoxy group is 100
% cyclotriphosphazene has a melting point of 154C, whereas the melting point of cyclotriphosphacene, in which 56 p-formylphenoxy groups and 44 phenoxy groups have been introduced, is significantly lower to 80C.

Such a phosphazene derivative into which a hol-7-enoxy group has been introduced has good compatibility with the epoxy resin, so it can be mixed with the epoxy resin at any ratio.
Due to the workability and properties of the cured product, the epoxy resin 1
It is preferably used in an amount of 10 to 400 parts by weight per 00 parts by weight.

Onium compounds and amines are preferably used as the curing accelerator. Examples of onium compounds include ammonium compounds, sulfonium compounds, iodonium compounds, and stannonium compounds. Furthermore, as ammonium compounds, for example, tetraethylammonium salt (((C2H5),N)+X-), tetrabutylammonium salt (((C,H,)4N)X-)
, As the sulfonium compound, for example, dimethyl-penzoylmethylsulfonium salt ((C6H, COCH2
S(CH3),)+X), diethyl-p-methoxypenzylsulfonium salt ((p-CH3QC,H4C
H2S (C2Hs) 2) +X"- '), as an iodonium compound, for example, diphenyliodonium salt (((C,H,)2I)"X-), as a stannonium compound, for example, tri7enyl stano Examples include nium salts (((C6H5) 3sn)+X-). However, X1 in the above chemical formula is BF4-, CJ-
, Br-, AsFs- and PF,-, etc.

Further, as the amines, tertiary amines, heterocyclic amines, and Lewis acid complexes thereof can be used.

Representative tertiary amines include triethylamine, triethanolamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, N,
N-diethylpenzylamine, N,N-dimethylaminobenzaldehyde, tris(dimethylaminomethyl)
Phenol and their BF3 complexes, heterocyclic amines such as imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, phenylimidazole, penzimidazole, pyridine, dimethylaminopyridine, piperidine, viperazine, and their BF3 complexes. can be mentioned.

Among the curing accelerators, onium compounds are known to easily generate cations when exposed to ultraviolet light or heat and become cationic polymerization initiators for epoxy resins. When used as an accelerator (thermally latent cationic catalyst), the activity is weak and the structure of the network is not sufficiently defined, so even if a large amount of curing accelerator is used, only a cured product with a low heat distortion temperature can be obtained. However, in the coexistence of the formylphenoxy group-introduced phosphazene derivative, the activity of the curing accelerator increases and curing proceeds even with a small amount, and the heat distortion temperature rises markedly depending on the blending ratio of the formylphenoxy group-introduced phosphazene derivative. . The desirable range of the amount of the curing accelerator added is 0.5 to 0.5 to the total amount of the epoxy resin and phosphazene derivative.
5. This is the weight section.

Furthermore, fillers, pigments, mold release agents, etc. can be added to the thermosetting resin composition of the present invention, if necessary. For example, fillers include calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, antimony oxide, gypsum, silica, alumina, clay talc,
graphite, molybdenum disulfide, mica, quartz powder,
Examples include, but are not limited to, iron powder, carbon plaque, carbon fiber, glass fiber, glass cloth, various types of paper, pulp, and wood powder.

The amount used can be selected as appropriate depending on the application, but the total amount of epoxy resin and phos-7azene derivative is 10
It can be used in a ratio of about 500 parts by weight to 0 parts by weight.

The mixing method for preparing the thermosetting resin composition of the present invention from each of the above components and the method for curing the prepared composition are not particularly limited, and various mixing methods and curing methods may be used. be able to.

Mixing methods include heating, melt mixing, mixing using rolls 1 or 21, mixing using an appropriate organic solvent,
and dry mixing.

In addition, the curing temperature during curing is 70 to 25O
r, preferably in the range of 120 to 2301:',
The curing time is 1 minute to 24 hours, preferably about 15 minutes to 15 hours. The curing may be performed in one step,
It may be carried out in two stages, such as partially curing the housing and then post-curing to complete the oven curing.

The cured product thus obtained exhibits excellent heat resistance.

(Effects of the Invention) The thermosetting resin composition of the present invention not only has good compatibility and excellent workability, but also has excellent mechanical properties that are comparable to cured products of conventional epoxy resin compositions. This provides a cured product that has strength and exhibits excellent heat resistance.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples. Of course, the present invention is not limited to these examples.

Example-1 43.5 parts by weight of hexa(p-formylphenoxy)cyclotriphosphazene and bisphenol A diglycidyl ether (Ebicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.)
After uniformly dissolving 56.5 parts by weight at 160C, 1
Lower the temperature to 30C and add diphenyliodonium tetrafluorobole} (((CsHs) 2 I)
BF 4- ) 2. 0 parts by weight was added and stirred for 10 minutes to obtain a resin composition.

This resin composition was soluble in ketone solvents and ether solvents, and could withstand long-term storage with almost no gelation at temperatures below 50C even in the state of solutions of b Resin 111 and resin combinations in various solvents. Then, this resin composition was poured into a mold and held at 180C for 30 minutes, then at 200C for 1 hour, and then held at 230C for 10 hours as post-curing to obtain a cast cured product. The heat distortion temperature (HDT') of this cured product is 240 C, bending strength 12-2 kg f/m2, bending modulus 410 kpf/m'', Rockwell hardness (M scale) 123.3, oxygen index 25.1. Met.

Example-2 30 parts by weight of hexa(p-formylphenoxy)cyclotriphosphazene, 70 parts by weight of Epicote 828 and di-7enyliodonium fluoroarsenate (
((06H5)2I)+ASF6-) From 3.0 parts by weight, a cast cured product was obtained in the same manner as in Example-1. The same physical properties as in Example-1 were measured, and the obtained results are shown in Table 1.

Example-3 70 parts by weight of hexa(p-formylphenoxy)cyclotriphosphazene, 30 parts by weight of Epicote 828 and dimethyl-benzoylmethylsulfonium tetrafluoroborate ([C6HsCOCH2S(CH3)
2) Practical example-1 from ``BF4-'' 3.0 parts by weight
A cast cured product was obtained in the same manner as above. Table 1 shows the results obtained by measuring the same physical properties as in Example-1.

Example 4 44.6 parts by weight of hexa(p-formylphenoxy)cyclotriphos-7azene, 55.4 parts by weight of phenol novolak diglycidyl ether (Epicote 154, manufactured by Yuka Shell Epoxy Co., Ltd.), and diphenyliodonium tetrafluoroborate A cast cured product was obtained from 2 parts by weight in the same manner as in Example-1.

The same physical properties as in Example-1 were measured and the results are shown in Table 1.

Example-5 50% p-formylphenoxy group and 5 phenoxy groups
0% substituted cyclotriphosphazene derivative 57.
9 parts by weight and 130 parts by weight of Ebiko}82842.1 parts by weight
After uniformly dissolving with C, 2.011 parts of diphenyl iodonium tetrafluoroborate was added and dissolved with stirring for 10 minutes to obtain a resin composition.

A cast cured product was obtained from this resin composition in the same manner as in Example-1. The same physical properties as in Example 1 were measured, and the obtained results are shown in Table 1.

Example-6 Casting in the same manner as in Example-1 from 43.5 parts by weight of hexa(0-formylphenoxy)cyclotriphosphazene, 56.5 parts by weight of Epicote 828, and 2.0 parts by weight of diphenyliodonium tetrafluoroborate. A cured product was obtained. Table 1 shows the results obtained by measuring the same physical properties as in Example-1.

Example 7 43.5 parts by weight of hexa(m-formylphenoxy)cyclotriphosphazene, 56.5 parts by weight of Epicote 828, and diphenyliodonium tetra. A cast cured product was obtained in the same manner as in Example 1 using 2.0 parts by weight of fluoroborate. Table 1 shows the results obtained by measuring the same physical properties as in Example-1.

Example-8 35.7 parts by weight of hexa(p-formylphenoxy)cyclotriphosphazene and 34.3 parts by weight of 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate (Araldite CY-179, manufactured by Ciba Geigy) After uniformly dissolving parts by weight at 130C,
Diphenyl iodonium tetrafluoroborate 2.0
Parts by weight were added and stirred at 130C for 10 minutes to obtain a resin composition.

This resin composite was soluble in ketone solvents and ether solvents, and could withstand long-term storage without gelling at temperatures below 50 C even when the resin composition was in the form of a solution in various solvents. Then, inject this resin composition into a mold 16
It was cured at 0C for 1 hour and then post-cured at 180C for 10 hours to obtain a cast cured product. The physical properties of this cured product were measured in the same manner as in Example 1, and the results are shown in Table 1.

Example-9 43.5 parts by weight of hexa(p-formyl-7-enoxy)tricyclophosphazene and 56.5 parts by weight of Epicote 828 were uniformly dissolved at 130C, followed by 1.0 parts by weight of 2-methylimidazole●BF3 complex. A cured resin product was obtained in the same manner as in Example-1. The same physical properties as in Example 11 were measured and the obtained results are shown in Table 1.

Example 10 After uniformly dissolving 17.4 parts by weight of hexa(p-formylphenoxy)cyclotriphosphazene and 22.6 parts by weight of Epicote 828 at 160C, the temperature was lowered to 130C and diphenyliodonium tetra 1.2 parts by weight of fluoroborate and 80 parts by weight of short glass fibers with an average length of 3 liters were added and heated to 130C for 10 minutes.
The mixture was kneaded for a minute to form a molding compound. Pour this compound into a specified mold and use a heated press to
Compression molding was carried out under conditions of 30 minutes at C and then 1 hour at 200 C. The resulting molded product was post-cured for 5 hours at 230C, and physical properties were measured.The bending strength was 25C.
．． 6kyf/w, flexural modulus 1930kPf/m2, H
It was DT285C.

Example-11 Instead of hexa(p-formylphenoxy)cyclotriphos-7acene in Example-1, 43.5 parts by weight of octa(p-formylphenoxy)cyclotetraphosphacene and 82856.5 parts by weight of Epicor The cast cured product was washed in the same manner as in Example-1 using the following.

The same physical properties as in Example-1 were measured, and the obtained results are shown in Table 1.

Comparative Example-1 Shrimp Coat 828 75.2 parts by weight and 4.4'-diaminodiphenylsulfone (DDS) 24.8 parts by weight 1
tl! After uniformly dissolving at 170C, the mixture was cooled to 120C, and 1.0 parts by weight of monoethylamine BF3 complex was added and dissolved with stirring to obtain a resin composition. This resin composition was poured into a mold at 120C for 1 hour, and then at 150C [1'2
Heat treatment was carried out for 200 C for 4 hours to obtain a cast cured product. This cured product is said to exhibit the highest heat resistance among amine cured products.

The same physical properties as in Example 1 were measured for this cured product, and the results are shown in Table 1.

Comparative Example-2 5.0 parts by weight of 2-methylimidazole/BF3 complex was added to 100 parts by weight of Epicoat 828, completely dissolved at room temperature, poured into a mold, heated at 200 t:' for 2 hours, and then heated at 230C. A cast cured product was obtained by heating for 5 hours.

The physical properties of this cured product were measured in the same manner as in Example 1, and the results are shown in Table 1. In this comparative example, curing was difficult if the amount of 2-methylimidazole•BF3 complex was 3.0 parts by weight or less.

Comparative Example-3 100 parts by weight of Ebicoat 828 and 2. After adding 0 parts by weight and completely dissolving it at room temperature, pour it into a mold and heat it at 200C for 2 hours.
The mixture was then heated at 230C for 5 hours to obtain a cast cured product. The physical properties of this cured product were measured in the same manner as in Example 1, and the results are shown in Table 1.

hand Continued Supplementary Positive -1 7. Contents of correction (1) Specification No. l Please refer to the appendix for the claims of page Heisei December 19, 1 year Correct it.

(2) Circular, page 5, 1 Correct the formula on line 0 as below. 1999 Patent Application No. 153193 Correct.

2. name of invention Record thermosetting resin composition 3. person who makes corrections Relationship with the incident

Claims (2)

[Claims] (1) Epoxy resin, a cyclophosphazene derivative having a formylphenoxy group represented by the general formula below; ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (However, n = 3 or 4, p + q = 2, p > 0, q ≧
0 and pn are positive integers, qn is 0 or a positive integer, and the formyl group may be located at any of the ortho, meta, and para positions of the benzene ring. ) or a mixture thereof and a curing accelerator as essential components. (2) 10 to 10 parts of a cyclophosphazene derivative having a formylphenoxy group is added to 100 parts by weight of the epoxy resin.
The thermosetting resin composition according to claim 1, characterized in that 400 parts by weight is blended.