JPH05148325A - Nonflammable resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in fire retardance, heat resistance and mechanical strength by compounding an alkenyl-phenol a maleimide and a specific compound. CONSTITUTION:The objective composition comprises an alkenylphenol, e.g. 2,2-bis[4-hydroxy-3-(2-methyl-2-propenyl)phenyl]propane, a maleimide, e.g. N,N '-(methylenedi-p-phenylene)dimaleimide; and a compound of formula I [wherein R<1> to R<4> are each a halogen or H and at least one is a halogen; (n) is 0 or 1; X is S, SO2, O, a group of formula II, or a group of formula C (R<5>) (R<6>) (wherein R<5> and R<6> are each H, an alkyl, phenyl, trifluoromethyl or trichloromethyl); and Y is H or an allyl] or a compound of formula III (wherein R<7> to R<11> are each a halogen or H and at least one is a halogen).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant resin composition useful for heat-resistant molded products, electric / electronic materials such as printed wiring boards, heat-resistant fillers and heat-resistant coating agents. The cured product is a flame-retardant resin composition having excellent properties such as flame retardancy, heat resistance, and mechanical strength.

[0002]

2. Description of the Related Art For electric and electronic parts represented by printed wiring boards, etc., in order to meet the demand for technological development aimed at large capacity, small size and light weight, high reliability and improved productivity. , A heat-resistant synthetic resin that is easy to mold is used.

A typical synthetic resin that forms a heat-resistant cured product that is easy to mold is a resin composition comprising a specific allyl compound such as alkenylphenol and a certain maleimide compound. However, these known resin compositions have drawbacks in flame retardancy against fire, especially in self-extinguishing properties when burned.

Therefore, in order to impart flame retardancy to a known resin composition, for example, a halogenated epoxy resin, a halogenated curing agent or the like is added to the compounding components of the allyl compound and the maleimide compound, which constitute the resin composition. Copolymerization is performed by adding a halogen-based flame retardant or a phosphorus-based flame retardant represented by phosphoric acid esters.

[0005]

The known resin composition to which the above flame retardant is added can give a certain degree of flame retardancy to a molded product obtained by curing the resin composition, but The heat resistance of the product tends to decrease, and when a halogenated compound of some kind is added as a flame retardant to the composition obtained by mixing the alkenylphenols and the maleimides, the alkenylphenols are converted to benzofuran derivatives. Since the polymerizable functional group is lost and affects various physical properties of the resulting copolymer resin, there are many problems to be solved, such as limiting the types of halogen-based flame retardants that can be used. There is.

[0006] In view of such a current situation, the present invention adds a specific flame retardant to a composition containing alkenylphenols and maleimides so that the cured product has flame retardancy and heat resistance. A flame-retardant resin composition having excellent properties such as properties and mechanical strength is provided.

[0007]

To achieve the above object, the flame-retardant resin composition of the present invention comprises an alkenylphenol (a), a maleimide (b) and the following general formula [1] or [2]. ] The compound shown by

[0008]

[Chemical 5]

[Wherein R ¹ , R ² , R ³ and R ⁴ are all halogen atoms or hydrogen atoms, at least one of them is a halogen atom, n is 0 or 1 and X is S, SO ₂ , O,

[0010]

[Chemical 6]

Or

[0012]

[Chemical 7]

(R ⁵ and R ⁶ are hydrogen atoms, alkyl groups,
A phenyl group, a trifluoromethyl group or a trichloromethyl group, which may be the same or different from each other. ) And Y is a hydrogen atom or an allyl group. ]

[0014]

[Chemical 8]

[In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are all halogen atoms or hydrogen atoms, and at least one of them is a halogen atom. ] It is characterized by consisting of and.

In the present invention, the alkenylphenols (a) constituting the flame-retardant resin composition are phenol derivatives having an alkenyl group, and as specific examples of preferable alkenylphenols, monovalent compounds represented by the following general formula [3] are used. The compounds derived from the above-mentioned phenols can be mentioned.

[0017]

[Chemical 9]

(In the formula, R ¹² , R ¹³ and R ¹⁴ are the same or different and represent an alkenyl group, an alkyl group, an alkoxy group,
It is an amino group, a nitro group or a halogen atom, and R ¹⁵ is an alkenyl group. )

Specific examples of the compound represented by the above general formula [3] include 2-allylphenol and 2-allyl-4-.
Methylphenol, 2-allyl-4-methoxyphenol, 2-allyl-6-methylphenol, 2-methallylphenol, 2-methallyl-4-methylphenol, 2
-Methallyl-4-methoxyphenol, 2-methallyl-
6-methylphenol, 2-crotylphenol, 2,
4-diallylphenol, 2,6-diallylphenol, 2,4,6-triallylphenol, 2,4-dimethallylphenol, 2,6-dimethallylphenol,
2,4,6-Trimethallylphenol, 2,6-diallyl-4-methylphenol and 2,6-dimethallyl-4
-Methoxyphenol and the like can be mentioned.

Other preferred alkenylphenols (a) include compounds derived from divalent phenols represented by the following general formula [4].

[0021]

[Chemical 10]

[Wherein R ¹⁶ and R ¹⁷ are the same or different and each represents a hydrogen atom, an alkenyl group, an alkyl group, an alkoxy group, an amino group, a nitro group or a halogen atom, and R ¹⁸
Is an alkenyl group, and X is S, SO ₂ , O,

[0023]

[Chemical 11]

Or

[0025]

[Chemical 12]

(Wherein R ¹⁹ and R ²⁰ are the same or different and are a hydrogen atom, an alkyl group, a phenyl group, a trifluoromethyl group or a trichloromethyl group), and n is It is 0 or 1. ]

Specific preferred examples of the compound represented by the general formula [4] include 2,2-bis [4-hydroxy-3-
(2-methyl-2-propenyl) phenyl] propane,
3,3-bis [4-hydroxy-3- (2-methyl-2)
-Propenyl) phenyl] pentane, 1,1,1,3
3,3-hexafluoro-2,2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane, 1,1,1,3,3,3-hexachloro-2,
2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] methane, 1,1-bis [ 4-hydroxy-3- (2-methyl-2-propenyl) phenyl] ethane, 4,4'-dihydroxy-3,3'-bis (2-methyl-2-propenyl) biphenyl, bis [4-hydroxy-3 -(2-Methyl-2-propenyl) phenyl] thioether, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] ether, bis [4-hydroxy-3-]
(2-methyl-2-propenyl) phenyl] sulfone,
2,2-bis [4-hydroxy-3- (2-propenyl) phenyl] propane, bis [4-hydroxy-3-
(2-Propenyl) phenyl] methane, 4,4'-dihydroxy-3,3'-bis (2-propenyl) biphenyl, bis [4-hydroxy-3- (2-propenyl) phenyl] thioether, bis [4- Hydroxy-3-
(2-propenyl) phenyl] ether, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfone, 2,2-bis [4-hydroxy-3- (2-butenyl) phenyl] propane, 2,2 -Bis [4-hydroxy-3,5-di (2-propenyl) phenyl] propane and 2,2-bis [4-hydroxy-3,5-di (2-
Methyl-2-propenyl) phenyl] propane and the like can be mentioned.

Further, as other preferable alkenylphenols (a), 1,1,1-tris (2-alkenyl-4-hydroxyphenyl) methane and 1,1,1-tris (2-alkenyl-4-hydroxy) are used. Phenyl) ethane and 4- {4- [1,1-bis (2-alkenyl-4)
Examples thereof include alkenylphenols derived from trivalent or higher valent phenols such as -hydroxyphenyl) ethyl]}-α, α-dimethylbenzylphenol.

Specific examples of preferable alkenyl groups in the alkenylphenols (a) include vinyl groups,
Allyl group, methallyl group, crotyl group and

[0030]

[Chemical 13]

And

[0032]

[Chemical 14]

There are groups represented by: and more preferable alkenyl groups are allyl group and methallyl group.

Specific preferred examples of the alkenylphenols of the present invention include 2,2-bis [4-hydroxy-
Examples thereof include 3- (2-methyl-2-propenyl) phenyl] propane and 2,2-bis [4-hydroxy-3- (2-propenyl) phenyl] propane.

Examples of the maleimides (b) include N-substituted maleimide compounds, N, N'-substituted maleimide compounds and prepolymers of these maleimide compounds, and these maleimide compounds may be used alone or in any combination thereof. More than one species can be used.

The N-substituted maleimide compound and N, N
Specific preferred examples of the ′ -substituted maleimide compound include:
N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide, N-hexyl maleimide, N-octyl maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-p-tolyl Maleimide, N-α-
Naphthyl maleimide, N-benzyl maleimide, Nm
-Tolylmaleimide, N-o-tolylmaleimide, N-
p-xylylmaleimide, Nm-xylylmaleimide, N-o-xylylmaleimide, N, N'-ethylenedimaleimide, N, N'-hexamethylenedimaleimide, N, N'-dodecamethylenedimaleimide , N-N '
-M-phenylene dimaleimide, N, N'-p-phenylene dimaleimide, N, N '-(oxydi-p-phenylene) dimaleimide, N, N'-(methylenedi-p-phenylene) dimaleimide, N, N ' -2,4-Tolylene dimaleimide, N, N'-2,6-tolylene dimaleimide, N, N'-m-xylylene dimaleimide, N, N '
-P-xylylene dimaleimide, N, N'-oxypropylene dimaleimide, ethylenedioxy-bis-N-propyl maleimide, oxy-bis-N-ethyl maleimide, N, N'-p, p'-diphenyl sulfone bis Maleimide, N, N'-p, p'-diphenyl ether bismaleimide, N, N'-dicyclohexylmethane bismaleimide, N, N '-(3,3'-dichloro-p, p'
-Bisphenylene) bismaleimide, 1,1,1,3
3,3-hexafluoro-2,2-bis (4-maleimidophenyl) propane and 1,1,1,3,3,3-hexafluoro-2,2bis [4- (4-maleimidophenoxy) phenyl] Propane etc. can be mentioned.

Preferred maleimides are N, N '.
Examples thereof include-(methylenedi-p-phenylene) dimaleimide and N, N'-p-phenylenedimaleimide.

The compound (c) in the present invention is added to the compound of the alkenylphenols (a) and the malemides (b) in order to impart flame retardancy to the resin composition and the molded articles obtained from them. A flame retardant to be added, which is a compound represented by the following general formula [1] or [2].

[0039]

[Chemical 15]

[Wherein R ¹ , R ² , R ³ and R ⁴ are all halogen atoms or hydrogen atoms, at least one of them is a halogen atom, n is 0 or 1 and X is S, SO ₂ , O,

[0041]

[Chemical 16]

Or

[0043]

[Chemical 17]

(R ⁵ and R ⁶ are hydrogen atoms, alkyl groups,
A phenyl group, a trifluoromethyl group or a trichloromethyl group, which may be the same or different from each other. ) And Y is a hydrogen atom or an allyl group. ]

[0045]

[Chemical 18]

[In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are all halogen atoms or hydrogen atoms, and at least one of them is a halogen atom. ]

Preferred examples of the halogen atom of the compound (c) in the present invention include chlorine atom and bromine atom.

Specific preferred examples of the compound (c) include tetrabromobisphenol A diallyl ether,
Tetrabromobisphenol A allyl ether, tribromobisphenol A diallyl ether, dibromobisphenol A diallyl ether, tetrabromobisphenol F diallyl ether, tetrabromobisphenol F allyl ether, tetrabromobisphenol S diallyl ether, tetrabromobisphenol S allyl ether, tetrachloro Bisphenol A diallyl ether, tetrachlorobisphenol A allyl ether,
Tetrachlorobisphenol F diallyl ether, bis (3,5-dibromo-4-allyloxyphenyl) thioether, bis (3,5-dibromo-4-allyloxyphenyl) ether, 1,1-bis (3,5-dibromo -4-allyloxyphenyl) cyclohexane, 2,
4,6-tribromophenol allyl ether, 2,4
-Dibromophenol allyl ether, 2,6-dibromophenol allyl ether, 2-bromophenol allyl ether, 3-bromophenol allyl ether,
4-bromophenol allyl ether, 2,4,6-trichlorophenol allyl ether, 2,3-dichlorophenol allyl ether, 2,5-dichlorophenol allyl ether, 4-chlorophenol allyl ether, 2,3,5-tri Examples thereof include fluorophenol allyl ether and 2,4,6-triiodophenol allyl ether, and if desired, one or more of the above compounds can be used as compound (c).

More preferable specific examples of the compound (c) include tetrabromobisphenol A diallyl ether and 2,4,6-tribromophenol allyl ether.

The preferable mixing ratio of the alkenylphenols (a) and the maleimides (b) is appropriately determined according to the purpose of use of the molded article to be obtained, but is based on 1 equivalent of the imide group of the maleimides. The alkenyl group of alkenylphenol is preferably in the range of 0.05 to 10 equivalents, more preferably in the range of 0.1 to 1.5 equivalents. If the amount of the alkenylphenol compounded is small, the cured product becomes brittle and the viscosity of the resin composition becomes high, so the moldability may decrease. On the other hand, alkenylphenols are 1
If it is more than 0 equivalent, the heat resistance may decrease.

The preferred addition amount of the compound (c) is 0. 0 with respect to 100 parts by weight of the mixture of the alkenylphenols (a) and the malemides (b) (hereinafter simply referred to as "parts").
It is in the range of 1 to 50 parts, more preferably 0.5 to 35.
It is a range of parts. If the addition amount is less than 0.1 part, it may be difficult to sufficiently exert the flame retardant effect, and if it is excessively added in excess of 50 parts, the heat resistance may decrease, which is not preferable.

The flame-retardant resin composition of the present invention may use a radical polymerization initiator such as an organic peroxide and an azo compound for the purpose of shortening the curing time.

Specific examples of the radical polymerization initiator include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide. , Cyclohexanone peroxide, dicumyl peroxide, bis (1-hydroxyheptyl) peroxide, t-butyl hydroperoxide, p-menthane hydroxyperoxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl perocto. Eight, t-butylperoxyisobutyrate and di-
Examples thereof include organic peroxides such as t-butyl perphthalate, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azo compounds such as methyl azobisisobutyrate. These can be used alone or in combination of two or more.

Further, for the purpose of increasing the mechanical strength of the obtained molded product, the flame-retardant resin composition of the present invention is added to a filler such as glass powder, fused silica, calcium carbonate or talc, glass cloth, quartz glass cloth, A reinforcing material such as carbon fiber cloth, paper or organic fiber cloth can be blended as necessary. The flame-retardant resin composition of the present invention can be easily obtained by uniformly mixing the above-mentioned various components by a conventional method regardless of the order of mixing.

The flame-retardant resin composition of the present invention can be cured by heat treatment at a temperature of about 100 to 300 ° C. for about 2 to 25 hours, and if necessary, the type of the radical polymerization initiator to be added. It is also possible to cure at a temperature of 100 ° C. or lower by appropriately adjusting the or blending amount.

[0056]

The flame-retardant resin composition of the present invention comprises a compound represented by the above general formula [1] or [2] in a mixture of an alkenylphenol (a) and a malemide (b) constituting the resin composition. Since (c) is blended as a flame retardant, the resin obtained by copolymerization has excellent heat resistance and flame retardancy. The resin having such flame retardancy has excellent heat resistance, flame retardancy and mechanical strength in its molded product.

[0057]

EXAMPLES Hereinafter, the flame-retardant resin composition of the present invention will be described more specifically with reference to Examples and Comparative Examples.

Example 1 As alkenylphenols (a), 10 parts of 2,2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane and maleimides (b) were used.
As a main component of a composition obtained by blending 11.8 parts of N, N '-(methylenedi-p-phenylene) dimaleimide.
2 parts of tetrabromobisphenol A diallyl ether was mixed as the compound (c) which is a flame retardant, and the mixture was stirred with heating to obtain a flame retardant resin composition as a uniform mixture. Next, 0.4 part of dicumyl peroxide was added at room temperature and well stirred, and the resin composition was put into a molding die made of ethylene tetrafluoride and heated at a temperature of 120 ° C. for 2 hours. A resin cured product was obtained by heat molding at 200 ° C. for 2 hours. As a result of thermogravimetric analysis (temperature rising rate: 20 ° C./min) of this resin cured product, the decomposition temperature in air was 432 ° C. Also, the tensile strength of the cured resin is 290 Kgf / c
It was m ² . Furthermore, as a result of the flame retardancy test measured according to JIS K6911 method B, the burning time was 1.5 seconds.

Examples 2 to 5 The same as Example 1 except that the type and addition amount of the alkenylphenols (a), maleimides (b) and compound (c) as a flame retardant of Example 1 were changed. And each flame-retardant resin composition of Examples 2-5 was obtained. These flame-retardant resin compositions were molded under the same conditions as in Example 1 and evaluated for the same physical properties.

Comparative Example 1 2,2-bis [4-hydroxy-3- (2-methyl-2)
-Propenyl) phenyl] propane 10 parts, N, N'-
(Methylenedi-p-phenylene) dimaleimide 10.7
The parts were mixed and stirred while heating to obtain a uniform resin composition. Then, dicumyl peroxide 0.38 at room temperature
Part was added and well stirred, and the resin composition was put into a molding die made of ethylene tetrafluoride, and the temperature was 120 ° C. using a hot press.
For 2 hours and then at 200 ° C. for 2 hours by heat molding to obtain a resin cured product. As a result of thermogravimetric analysis (temperature rising rate of 20 ° C./min) of the resin cured product, the decomposition temperature in air was 440 ° C.
Met. The tensile strength of the cured resin is 280 Kgf.
Was / cm ² . Further, as a result of the flame retardancy test measured according to JIS K6911 method B, the burning time was 30 seconds or more.

Comparative Example 2 2,2-bis [4-hydroxy-3- (2-methyl-2)
-Propenyl) phenyl] propane 10 parts, N, N'-
(Methylenedi-p-phenylene) dimaleimide 10.7
The parts were mixed and stirred while heating to obtain a uniform resin composition. This resin composition was placed in a tetrafluoroethylene mold equipped with a hot press in the same manner as in Example 1, and the temperature was 120.
C. for 2 hours, then at 200.degree. C. for 2 hours and then at 220.degree. As a result of thermogravimetric analysis (temperature rising rate: 20 ° C./min) of this resin cured product, the decomposition temperature in air was 427 ° C. The tensile strength of the resin cured product was 300 Kgf / cm ² .
Further, as a result of the flame retardancy test measured according to JIS K6911 method B, the burning time was 30 seconds or more. Table 1 below shows the evaluation results of the composition of each of Examples 1 to 5 and Comparative Examples 1 and 2 and the physical properties of the cured resin.

[0062]

[Table 1]

Note) Top: compound; bottom: compounding amount (parts by weight)

The symbols in the table indicate the following compounds. (A); Alkenylphenols (a) 1; 2,2-bis [4-hydroxy-3- (2-
Methyl-2-propenyl) phenyl] propane (a) 2; 2,2-bis [4-hydroxy-3- (2-
Propenyl) phenyl] propane (b); Maleimides (b) 1; N, N '-(methylenedi-p-phenylene)
Dimaleimide (b) 2; N-phenylmaleimide (c); flame retardant (c) 1; tetrabromobisphenol A diallyl ether (c) 2; 2,4,6-tribromophenol allyl ether (d); organic Peroxide (d) 1; Dicumyl peroxide

Example 6 A flame-retardant resin composition was obtained in the same manner as in Example 1 except that dicumyl peroxide was not added. Next, 0.4 part of dicumyl peroxide was added and stirred well at room temperature, and the resin composition was put into a molding die made of ethylene tetrafluoride and heated at a temperature of 120 ° C. for 2 hours. A resin cured product was obtained by heat molding at 200 ° C. for 2 hours.
This resin composition was placed in a tetrafluoroethylene mold equipped with a hot press in the same manner as in Example 1, and the temperature was 120 ° C. for 2 hours, then the temperature was 180 ° C. for 2 hours, and the temperature was 22 ° C.
A resin cured product was obtained by heat molding at 0 ° C. for 2 hours. As a result of thermogravimetric analysis (temperature rising rate: 20 ° C./min) of this resin cured product, the decomposition temperature in air was 425 ° C. The tensile strength of the resin cured product was 310 Kgf / cm ² . Furthermore, as a result of the flame retardancy test measured according to JIS K6911 method B, the burning time was 1.8 seconds.

[0066]

The flame-retardant resin composition of the present invention comprises a composition mainly composed of an alkenylphenol (a) and a maleimide (b), and the above-mentioned general formula [1] or [1] as a flame retardant. [2] The resin composition is formed by mixing the compound (c) shown in [2], and the cured resin obtained after curing has excellent heat resistance, flame retardancy and mechanical strength. It is possible to achieve flame retardancy in electrical and electronic materials such as, and other heat-resistant molded products, and its industrial value is extremely large.

Continued Front Page (72) Inventor Kaoru Kimura 1-1 Funami-cho, Minato-ku, Aichi Prefecture Nagoya City Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute

Claims (1)

[Claims] 1. A flame-retardant resin composition comprising an alkenylphenol (a), a maleimide (b) and a compound represented by the following general formula [1] or [2]. [Chemical 1] [Wherein R ¹ , R ² , R ³ and R ⁴ are each a halogen atom or a hydrogen atom, at least one of them is a halogen atom, n is 0 or 1, and X is S or S.
O ₂ , O, embedded image Or (R ⁵ and R ⁶ are a hydrogen atom, an alkyl group, a phenyl group,
A trifluoromethyl group or a trichloromethyl group,
They may be the same as or different from each other. ),
Y is a hydrogen atom or an allyl group. ] [Chemical 4] [In the formula, each of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is a halogen atom or a hydrogen atom, and at least one of them is a halogen atom. ]