JPH09324108A - Flame-retarded resin composition and laminated board made thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new halogen-free thermosetting resin flame-retarding system realizing high flame-retardancy and free from the deterioration of moisture resistance and other properties of the product without using a halogen compound. SOLUTION: This flame-retarded resin composition is composed of (A) an epoxy resin having >=2 epoxy groups in one molecule (excluding halogenated epoxy resin), (B) one or more resins selected from a maleimide compound having one or more maleimide groups in one molecule, a cyanate compound having >=2 cyanate groups in one molecule and an isocyanate compound having >=2 isocyanate groups in one molecule and (C) a compound containing phosphorus atom. The composition has a nitrogen content of 1-10wt.% and a phosphorus content of 0.5-6wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition. The flame-retardant resin composition of the present invention is to provide a novel non-halogen thermosetting resin flame-retardant system corresponding to the trend of times when environmental issues are emphasized.

[0002]

2. Description of the Related Art The flame retardancy of resins for electronic materials such as copper-clad laminates and IC encapsulation materials is an essential property in terms of product safety. Thermosetting resins used in this field are epoxy resins and the like, but conventionally, halogen-containing compounds such as brominated epoxies have been generally used to make these resins flame-retardant. However, recently, the tendency toward eco-materials and green materials has become stronger, especially in Europe, and as a part of that, there is a movement to stop using halogen-containing flame retardants. It is a well-known fact that studies on the use of phosphorus compounds as alternative flame retardants have been widely conducted in order to respond to such trends. However, when the phosphorus compound is used alone in the epoxy resin system, a large amount of the phosphorus-based flame retardant must be added in order to satisfy the flame retardance, and thus the physical properties of the cured product are deteriorated or the hydrolysis of the phosphorus compound is caused. Problems such as deterioration of the moisture resistance of the product have occurred.

[0003]

The present invention has been made as a result of extensive studies to solve the above-mentioned problems, and realizes good flame retardancy without using a halogen compound and has a moisture resistance of a product. The present invention provides a novel halogen-free thermosetting resin flame-retardant system without deterioration of properties and other physical properties.

[0004]

The present invention provides (A) an epoxy resin having at least two epoxy groups in one molecule and excluding halogenated epoxy resin, and (B) a maleimide group in one molecule. A maleimide having at least one
Cyanate having at least two cyanate groups in one molecule and at least two isocyanate groups in one molecule
1 selected from the group consisting of isocyanates having 1 or more
A resin composition comprising at least one resin and (C) a phosphorus atom-containing compound, and having a nitrogen content of 1 wt% to 10 wt% and a phosphorus content of 0.5 wt% to 6 wt% And a laminated board using the same.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, making an epoxy resin flame-retardant using a phosphorus compound alone adversely affects the physical properties and moisture resistance of the cured product because it is necessary to add a large amount of phosphorus. In order to solve such a problem in the present invention,
Flame retardancy by coexistence of phosphorus and nitrogen Reduce phosphorus content by utilizing synergistic effect, reduce phosphorus content with improvement of flame retardance by introducing nitrogen-containing ring structure and improve physical properties of cured product, and further specific hydrolysis resistance The technical gist is to improve the moisture resistance by introducing and adding a good phosphorus compound.

The epoxy resin (A) having at least two epoxy groups in one molecule and excluding halogenated epoxy resin in the present invention is bisphenol A type epoxy, bisphenol F type epoxy, phenol novolac type epoxy, cresol. Novolac type epoxy,
Examples thereof include naphthalene type epoxy, biphenyl type epoxy, triglycidyl isocyanurate, etc., but are not particularly limited thereto. However, since the present invention proclaims a non-halogen thermosetting resin flame-retardant system that does not use a halogen-based flame retardant, halogen-containing epoxies such as brominated bisphenol A epoxy and brominated novolac epoxy are excluded. However, chlorine contained in ordinary epoxy resins derived from epichlorohydrin is unavoidably mixed. However, the amount is several hundred ppm with hydrolyzable chlorine at a level known to those skilled in the art.
Is the order.

The maleimide having at least one maleimide group in one molecule of the component (B) used in the present invention is N-methylmaleimide, N-butylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide. , N-cyclohexylmaleimide, N
-Phenylmaleimide, N- (o-tolyl) maleimide, N-dodecylphenylmaleimide, N-chlorophenylmaleimide, N-dichlorophenylmaleimide, N
-(O- or p-hydroxyphenyl) maleimide,
N- (o- or m-methoxyphenyl) maleimide,
N- (m-hydroxycarbonylphenyl) maleimide, N- (m-nitrophenyl) maleimide, 1-methyl-2,4-bismaleimidobenzene, N, N'-m-
Phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m-toluylene bismaleimide, N, N'-4,4'-biphenylene bismaleimide, N, N'-4,4 '-[3,3'-Dimethyl-biphenylene] bismaleimide, N, N'-4,4'-
[3,3′-Dimethyldiphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, N, N′-4,4′-diphenylmethane bismaleimide, N, N'-4,4'-
Diphenylpropane bismaleimide, N, N'-4,
4'-diphenyl ether bismaleimide, N, N'-
3,3′-diphenylsulfone bismaleimide, N,
N'-4,4'-diphenylsulfone bismaleimide,
2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-t-butyl-4-
(4-maleimidophenoxy) phenyl] propane,
2,2-bis [3-s-butyl-4- (4-maleimidophenoxy) phenyl] propane, 1,1-bis [4-
(4-maleimidophenoxy) phenyl] decane, 1,
1-bis [2-methyl-4- (4-maleimidophenoxy) -5-t-butylphenyl] -2-methylpropane, 4,4'-cyclohexylidene-bis [1- (4-
Maleimidophenoxy) -2- (1,1-dimethylethyl) benzene], 4,4′-methylene-bis- [1-
(4-maleimidophenoxy) -2,6-bis (1,1
-Dimethylethyl) benzene], 4,4'-methylene-
Bis [1- (4-maleimidophenoxy) -2,6-di-s-butylbenzene], 4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2-cyclohexylbenzene], 4 , 4'-methylene-bis [1- (maleimidophenoxy) -2-nonylbenzene], 4,4 '-(1-methylethylidene) -bis [1
-(Maleimidophenoxy) -2,6-bis (1,1-
Dimethylethyl) benzene], 4,4 '-(2-ethylhexylidene) -bis [1- (maleimidophenoxy)]
-Benzene], 4,4 '-(1-methylheptylidene)
-Bis [1- (maleimidophenoxy) -benzene],
4,4'-Cyclohexylidene-bis [1- (maleimidophenoxy) -3-methylbenzene], 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy)
Phenyl] hexafluoropropane, 2,2-bis [3
-Methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-
Maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4- Maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-ethyl-4- (4
-Maleimidophenoxy) phenyl] hexafluoropropane, bis [3-methyl- (4-malemidophenoxy) phenyl] methane, bis [3,5-dimethyl- (4
-Maleimidophenoxy) phenyl] methane, bis [3
-Ethyl- (4-maleimidophenoxy) phenyl] methane, 3,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5,2,1,0 ^2.6 ]
Decane, 4,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5,2,1,0 ^2.6 ]
Decane, 3,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5,2,1,0 ^2.6 ]
Decane, 4,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5,2,1,0 ^2.6 ]
Examples include decane, but heat resistance, price, supply stability,
Aromatic bismaleimides and N-substituted aromatic monomaleimides are preferable from the viewpoint of versatility, and N, N′-4,
4'-diphenylmethane bismaleimide is preferred. Further, it is possible to use Michael addition with amines and ene reaction products with allyl compounds to adjust the solubility of maleimide in a solvent and the crosslinking density.

The cyanate having at least two cyanate groups in one molecule used in the present invention includes 2,2-bis (4-cyanatephenyl) propane, di (4-cyanate-3,5-dimethylphenyl) methane and cyanate. It is not particularly limited as long as it is a cyanate derived from a phenol compound and a cyanogen halide, such as a derivatized phenol novolac and a cyanated dicyclopentadiene-modified phenol novolac.
-Bis (4-cyanatephenyl) propane, di (4-
Cyanate-3,5-dimethylphenyl) methane and cyanated phenol novolac are preferred. Further, there is no problem even if a precyclization reaction product with an oligomer or epoxy obtained by partial trimerization of the above cyanate is used.

Examples of the isocyanate having at least two isocyanate groups in one molecule used in the present invention include toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylene diisocyanate, n-alkane both-end diisocyanate, and hexahydroxyxylene diisocyanate. However, general-purpose toluene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate are more preferable. Further, a partially trimerized oligomer of these isocyanates, an oxazolidone ring-containing product by a partial reaction with an epoxy resin, a partially blocked isocyanate by a hydroxy group-containing compound (including a hydroxyl group-containing bisphenol A epoxy), etc. are included in the scope of the present invention.

The phosphorus compound used in the present invention may be any one containing a phosphorus atom, and known phosphorus-based flame retardants such as phosphates such as tri-substituted phosphate, phosphine oxides such as tri-substituted phosphine oxide, red phosphorus and the like. Examples include microencapsulated products and phosphazene derivatives. Considering physical properties such as heat resistance of the cured product and moisture resistance, those that are reactive with the resin matrix or have self-polymerization are preferable, and they are directly bonded to the phosphorus atom. A functional group selected from the group consisting of active hydrogen group, amino group not directly bonded to phosphorus atom, hydroxyl group, epoxy group, maleimide group, cyanate group, isocyanate group, acryl group, and methacryl group. A phosphorus compound having at least one phosphorus compound in one molecule is preferable, and for example, phosphorus trichloride can be used. Etc. and oxy those such as polyfunctional phenol chloride phosphate or trialkyl phosphates and reacted it is preferred synthesis is simple.

Further, 9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as HCA) is reactive with the resin matrix, and tris (3-aminophenyl) phosphine oxide (hereinafter abbreviated as TAPO) is hydrolysis resistant and resin matrix. In terms of reactivity with hexamethacryloyloxyethoxycyclotriphosphazene (hereinafter abbreviated as PPZ)
Is preferable in terms of self-polymerization property, hydrolysis resistance, and reactivity with a resin matrix.

Since HCA has an active hydrogen group directly bonded to a phosphorus atom in the molecule, if its reactivity is utilized, P-H of HCA may be added to the double bond of the maleimide group during curing, Since a dehydration reaction between the hydroxyl group and PH occurs,
It is preferable because it is firmly bonded to the resin matrix.

In the present invention, the nitrogen and phosphorus contents in the resin composition are important factors, which have been described so far (A).
An epoxy resin having at least two epoxy groups in one molecule and excluding a halogenated epoxy resin, and (B) 1
One or more resins selected from the group consisting of a maleimide having at least one maleimide group in the molecule, a cyanate having at least two cyanate groups in the molecule, and an isocyanate having at least two isocyanate groups in one molecule. And (C) a resin composition comprising a phosphorus atom-containing compound and having a nitrogen content of 1% by weight or more and 10% by weight or less and a phosphorus content of 0.5% by weight or more and 6% by weight or less. It is possible to achieve both flame retardancy and heat resistance, moisture resistance and other properties of the cured product without using. If the nitrogen content exceeds 10% by weight (hereinafter,% by weight is abbreviated as%), the water absorption becomes too large and the resin cured product becomes brittle, which is not preferable. Further, if the nitrogen content is less than 1%, a large amount of phosphorus compound must be added in order to realize flame retardancy, and heat resistance and moisture resistance are reduced. If the phosphorus content is less than 0.5%, it becomes difficult to achieve flame retardancy,
If it exceeds 6%, the heat resistance and the moisture resistance are lowered and the flame resistance is unstable.

The phosphorus used in the present invention captures oxygen in the air or resin during combustion to generate phosphoric acid, which is further dehydrated to form polyphosphoric acid to form a film on the surface of the cured product and supply oxygen to the combustion section. Shut off, prevent the spread of fire. In this mechanism, the nitrogen contained in the resin has the effect of promoting the dehydration condensation of this phosphoric acid, and has the effect of reducing the minimum amount of phosphorus required for flame retardancy. Further, maleimide, cyanate, and isocyanate, which are nitrogen-containing resins used in the present invention, have an inherent nitrogen-containing ring (maleimide ring) or an epoxy group such as a triazine ring, an isocyanurate ring, or an oxazolidone ring generated at the time of curing. It is another important factor for flame retardancy to include a ring structure formed by reaction in the cured structure. That is, these cured structures have a high thermal decomposition temperature and not only have the property of not burning themselves,
This is because it has a high heat resistance and has a function of offsetting the decrease in heat resistance due to the addition of the phosphorus compound.

In the present invention, if necessary, those known to those skilled in the art as curing agents for epoxy resins such as amines, phenolic resins, dicyandiamide and acid anhydrides and curing accelerators for imidazole, cobalt naphthenate, tin compounds and the like can be used. There is no problem in using it, and there is no problem in using a glass cloth, a copper foil, or the like which is known to those skilled in the art and is necessary for producing a copper-clad laminate. Examples will be shown below, but the invention is not limited thereto.

[0016]

【Example】

(Synthesis example 1) 53.2 g of tributyl phosphate was placed in a 300 ml separable flask equipped with a stirrer and a cooling tube.
(0.2 mol), 83.2 g (OH 0.8 mol) of phenol novolac PR-51470 manufactured by Sumitomo Durez Co., Ltd.
The mixture was put in, reacted by heating at 130 ° C. for 3 hours, and then continuously stirred under reduced pressure for 1 hour at the same temperature, and then the content was taken out to obtain a product TBPPN. The phosphorus content of TBPPN was 6.1%.

(Synthesis Example 2) Journal of Applied Polymer
A tris (3-aminophenyl) phosphine oxide TAPO was prepared by introducing an amino group into triphenylphosphine oxide by the method described in Science, 59, 215 (1996).
Was synthesized. The phosphorus content of this compound was 9.6%.

(Example 1) 22 parts by weight of phenol novolak Epicron N-770 manufactured by Dainippon Ink and Chemicals Co., Ltd., 42.5 parts of DDM type bismaleimide BMI-H manufactured by KI Kasei Co., Ltd., 13.5 parts of diaminodiphenylmethane and 22 parts of triphenyl phosphate were dissolved in 100 parts of a mixed solvent of N, N-dimethylformamide and 1: 1 of methyl ethyl ketone to prepare a varnish having a concentration of 50% by weight. This varnish was impregnated into 100 micron glass cloth and dried at 150 ° C. for 4 minutes to obtain a prepreg having a resin content of 40% by weight. 16 pieces of this prepreg are piled up, a 35-micron-thick copper foil is piled on the outside, and sandwiched between two stainless steel plates, 170 ° C, 40 kg / cm ²
After pressing for 2 hours, a double-sided copper-clad laminate having a thickness of 1.6 mm was obtained. The obtained laminated board was subjected to UL flame resistance test and solder heat resistance test as shown in Table 1. The results are shown in Table 1. This laminated plate cleared UL-94 V-0, and further had a good result after the A treatment and the moisture absorbing solder float for 180 seconds.

[0019]

[Table 1] 1) Weight% of N and P contained in resin 2) Phenol novolac epoxy manufactured by Dainippon Ink and Chemicals 3) Bisphenol A epoxy manufactured by Yuka Shell Epoxy 4) Triglycidyl isocyanurate manufactured by Nissan Chemical Industries 5) Keisei Kasei Manufactured by diaminodiphenylmethane type bismaleimide 6) manufactured by Daihachi Chemical Co., Ltd. N-4-hydroxyphenylmaleimide 7) Synthetic Example 1 8) manufactured by Sanko Chemical Co., Ltd. 9) Synthetic Example 2 10) manufactured by Kyoei Chemical Co., Ltd.

[0020]

[Table 2] 1) Weight% of N and P contained in resin 2) Asahi Ciba bisphenol A type cyanate ester 3) -OCN equivalent 129 phenol novolac type cyanate ester 4) Dainippon Ink and Chemicals phenol novolak

[0021]

[Table 3] 1) Weight% of N, P contained in resin 2) Diphenylmethane diisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd. 3) Naphthalene diisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd. 4) Diphenyl monophenol phosphate manufactured by Daihachi Chemical Industry Co., Ltd.

[0022]

[Table 4] 1) Weight% of N and P contained in the resin

[0023]

[Table 5]

(Examples 2 to 18 and Comparative Examples 1 to 7) Using the formulations shown in Tables 1 to 5, copper-clad laminates were prepared in the same manner as in Example 1 and subjected to a flame resistance test and a solder heat resistance test. The results are shown in Tables 1 to 5. The laminated plates having the formulations shown in the examples are all excellent in flame resistance and solder heat resistance. On the other hand, Comparative Examples 1, 4, 6
Has too much phosphorus component and the heat resistance is lowered. Further, in Comparative Examples 2 and 5, since the nitrogen content is too high and the moisture absorption is large, the moisture absorbing solder is defective. In Comparative Example 3, the phosphorus content is too much and the flame resistance and heat resistance are lowered. In Comparative Example 7, both the nitrogen and phosphorus components were too small and the flame resistance decreased.

[0025]

EFFECTS OF THE INVENTION The flame-retardant resin composition of the present invention is non-halogen and has excellent flame resistance, heat resistance, and humidity resistance, and the current environmental trends are becoming more important. The present invention provides a resin composition useful as a new ecomaterial corresponding to the above.

Claims (8)

[Claims] 1. (A) Epoxy resin having at least two epoxy groups in one molecule and excluding halogenated epoxy resin; (B) Maleimide having at least one maleimide group in one molecule; A resin comprising one or more resins selected from the group consisting of cyanates having at least two cyanate groups in the molecule and isocyanates having at least two isocyanate groups in one molecule, and (C) a phosphorus atom-containing compound. The composition has a nitrogen content of 1% by weight or more and 10% by weight or less and a phosphorus content of 0.
A flame-retardant resin composition, which is 5% by weight or more and 6% by weight or less. 2. A laminate comprising the flame-retardant resin composition according to claim 1 and a substrate. 3. The flame-retardant resin composition according to claim 1, wherein the maleimide as the component (B) is an aromatic bismaleimide and / or an N-substituted aromatic monomaleimide. 4. The maleimide of the component (B) is N, N′-
The flame-retardant resin composition according to claim 1, which is 4,4′-diphenylmethane bismaleimide. 5. The component (B) cyanate is at least one selected from the group consisting of 2,2-bis (4-cyanatephenyl) propane, di (4-cyanate-3,5-dimethylphenyl) methane and cyanated phenol novolac.
The flame-retardant resin composition according to claim 1, which is a cyanate selected from species. 6. The flame-retardant resin composition according to claim 1, wherein the isocyanate as the component (B) is an isocyanate selected from at least one selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate. 7. The phosphorus compound is an active hydrogen group directly bonded to a phosphorus atom, an amino group not directly bonded to a phosphorus atom, a hydroxyl group, an epoxy group, a maleimide group, a cyanate group, an isocyanate group, an acryl group and methacryl. The flame-retardant resin composition according to claim 1, which is a phosphorus compound having at least one functional group selected from the group consisting of groups in one molecule of the phosphorus compound. 8. The phosphorus compound is 9,10-dihydro-9-
The resin composition according to claim 1, which is a phosphorus compound selected from at least one selected from the group consisting of oxa-10-phosphaphenanthrene-10-oxide, tris (3-aminophenyl) phosphine oxide, and hexamethacryloyloxyethoxycyclotriphosphazene. Stuff.