JPS581682B2 - Thermosetting flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant resin composition for electrical insulation, and particularly to a heat-resistant resin composition that has excellent high-frequency electrical properties, moisture resistance, and dimensional stability.

Traditionally, 1,2 polybutadiene has been applied to various electrical insulating material phases because of its excellent dielectric properties, heat resistance, and moisture resistance. Adhesiveness to adhesives, reinforcing agents, or metals was insufficient.

Various modified 1 and 2 polybutadienes have been proposed to solve these problems, but on the contrary, these have the disadvantages of slow curing speed and poor reactivity, or because they have been modified,
The excellent heat resistance of l.2 polybutadiene homopolymer was lost.

Moreover, even with these modifications, it has not been possible to solve the disadvantages of 1,2 polybutadiene in terms of dimensional stability, especially large thermal expansion.

In order to solve these drawbacks, the inventors first filed a patent application in 1973.
-146859, Japanese Patent Application No. 146860, Japanese Patent Application No. 53-146861, Japanese Patent Application No. 1983
-146862, etc., by imide modification of 1,2 polybutadiene to improve adhesion and further improve dimensional stability without impairing the excellent heat resistant dielectric properties of 1,2 polybutadiene. However, the resins related to these applications are flammable.

Recently, there has been a strong demand for flame retardancy in electronic communication equipment, and the present invention is intended to address this flame retardancy.

Conventionally, brominated aromatics (hexabromobenzene, decabrom diphenyl, decabrom diphenyl ether, etc.) and phosphoric acids (triphenyl phosphate and its bromine compounds, etc.) have been used as flame retardants for molding materials. However, they all have problems with heat resistance during laminated molding, blistering between layers during soldering heat resistance, inhibiting the curing reaction of 1,2-polybutadiene resin and imide compound during molding, and bleed of flame retardant onto the surface of the laminate. It was not satisfactory as a flame retardant for laminates mainly composed of 1,2-polybutadiene resin such as OUT.

The object of the present invention is to improve the above-mentioned drawbacks and to provide an imide-modified 12-polybutadiene resin laminate with a strong flame retardant effect.

A butadiene polymer containing 50% or more in the polymer chain of 1,2-butadiene units having side chain double bonds and general formula [A]
It is indicated by.

[R represents a divalent hydrocarbon group having at least 2 carbon atoms] A bismaleimide compound and a 2,4,6-tribromophenyl compound represented by the general formula [B] or an acryloyl group in the molecule or a general formula having two methacryloyl groups [wherein X is Br or Cl Y is H or CH3 m, n is an integer from 1 to 4 A is -, -O-, -CO-, -SO2-, (b is 1
(an integer of ~4)] This is achieved by a thermosetting flame-retardant resin composition obtained by thermally curing a mixture consisting of a compound represented by the following formula in the presence of an organic peroxide.

The present invention will be explained in detail below.

In the present invention, cured 1.2-polybutadiene, which is a heat-resistant resin composition, is composed of (1) a putadiene polymer containing 50% or more of 1.2-putadiene units having side chain double bonds in the polymer chain, and the general formula (A ).

[R represents a divalent hydrocarbon group having at least 2 carbon atoms] Comprising a bismaleimide compound and a compound represented by formula B or a compound represented by formula C, which is thermally cured in the presence of an organic peroxide. or (2) 20 obtained by heating a mixture of the bismaleimide compound of the general formula [A] and the diamine in a molar ratio practically equal to 1.
a bismaleimide grepolymer having a melting point of 0°C or less;
The above butadiene polymer and a 2,4,6 tripromphenyl compound represented by formula B or a compound having two acryloyl or methacryloyl groups represented by formula C are heated in the presence of an organic peroxide. Obtained by curing.

Next, a method for producing a flame-retardant laminate (resin composition) using a 2,4,6-tribromophenylene compound of formula B according to the present invention will be described.

A resin mainly composed of 1,2 polybutadiene having a polymerizable double bond in the side chain and an imide compound are dissolved in an organic solvent, and then, for example, benzoyl peroxide, t-butyl peroxybenzoate, t-butyl peroxybenzoate, etc. peroxides such as dicumyl peroxide, di-t-butylperoxybutarate, t-butylperoxy-2-ethylhexanoate, dicumyl peroxide, azo compounds such as azoisobutyronitrile and benzenediazonium, and other radical polymerization catalysts. Prepare a face consisting of a 2,4,6 tribromophenyl compound represented by formula B and antimony trioxide, or triphenylantimony, or molybdenum trioxide preferably having a particle size of 10 μm or less, and apply the present varnish. A prepreg sheet is produced by impregnating a base material, such as a cloth or nonwoven fabric using organic or inorganic fibers such as glass fiber or synthetic fiber, and then evaporating the solvent and drying it.

By stacking these prepreg sheets and, in the case of copper-clad laminates, further stacking copper foil on top and bottom, heating and processing, 1.
Flame retardant, heat resistant, To produce a laminate or copper-clad laminate with good lead-out resistance.

The laminates obtained by this method have good compatibility with the flame retardant and resin, and because they are copolymerized, the electrical and mechanical properties required for laminates are also extremely good. is stable.

Furthermore, in the 2,4,6 tribromo phenyl compound, the polar atom bromine is bonded to the benzene nucleus in a well-balanced manner, so the polarity of the molecule as a whole cancels out and the dielectric constant increases only slightly.

Next, a flame-retardant resin composition using the compound of formula C according to the present invention will be explained.

As 1,2-polybutadiene, the average molecular weight is 100
0 to 5,000 and exhibits a viscous liquid state at room temperature, and those with an average molecular weight of 50,000 to 2,000.
00, a thermoplastic, high molecular weight material with a melting point of 50 to 200° C. can be used, and both are easily crosslinked and cured in the presence of a conventional organic peroxide curing agent.

Further, in the bismaleimide compound of general formula (A), the symbol R represents a linear or branched alkylene group, phenylene or cyclohexylene group, or a group having less than 13 carbon atoms.

Further, the symbol R represents a divalent group or atom, such as an oxygen atom,
Sulfur atom, alkylene group having 1 to 3 carbon atoms, or -CO-, -SO2-, -NR1-, -N=
It can be a polyaromatic group or a polyalicyclic group bonded by a group represented by N-, -COO-, -CONH-, -P-CONH-, -P(O)-R1, or the like.

In the above formula, R1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl or cyclohexyl group.

The compound represented by the general formula C may be used as it is, or may be used as a polymer of two or more molecules.

Moreover, these can also be used as a mixture of two or more types.

Examples of curved forms of compounds represented by the general formula are as follows.

2,2-bis(4-methacryloyl-3,5-dibrophenyl)propane 2,2-bis(4-acryloyl-3,5-dibromophenyl)furopane 2,2-bis(4-methacryloyl-3,5) -dichlorophenyl)furopane2,2-bis(4-acryloyl-3,5-dichlorophenyl)propane4,4'-diacryloyl-3,3',5,5'-tetrabromodiphenylsulfone4, 4'-dimethacryloyl-3,3'-dichlorodiphenylsulfone 4,4'-dimethacryloyl-3,3',5,5'-
Tetrapromodiphenylmethane 4,4'-dimethacryloyl-3,3',5,5'-
Tetrabromodiphenylketone 4,4'-dimethacryloyl-3,3'-dibromodiphenylbutane 4,4'-dimethacryloyl-2,2,3,3',5
・5′・6・6′-octachlorophenyl ether 4・
4'-diacryloyl-3,3',5,5'-tetrachlorodiphenyl Also, curved examples of organic peroxides useful in the present invention include penzoyl peroxide, 1,1-bis- t-Butylperoxy-3,3,5-trimethylcyclohexane, dicumyl peroxide, t-butylperoxybenzoate, di-t-butylperoxide, t-butylperoxybenzoate, di-t-butylperoxybenzoate isopyrbenzene, 2,5-dimethyl-2,5-
Examples include di-t-butylperoxyhexane-3.

The flame-retardant resin composition of the present invention not only has an excellent flame-retardant effect, but also hardly deteriorates the original electrical properties and other physical properties of 1,2-polyptadiene, so it is suitable for electrical and electronic parts. It has excellent performance as an applied electrical insulation material.

Furthermore, the resin composition of the present invention exhibits stable self-extinguishing properties even after being ignited several times, and has extremely long-lasting flame retardancy.

The invention will now be further explained by way of examples.

Example 1 Attractive 1,2-polyptadiene (number average molecular weight of about 1,500
, product name NISSO-PB-B1000, Nippon Soda) 4
0 g, N・N′-4・4′-diphenylmethane bismaleimide 30 g, 2・4・6 tribromo phenyl methacrylate 30 g, and dicumyl peroxide 5 g at 80°C.
were uniformly stirred and mixed in a liquid state to obtain a homogeneous mixture.

This was poured into a Teflon mold that had been kept at a temperature of 100℃ in advance, and after degassing under vacuum,
Heat curing was carried out from 10°C to 200°C for 2 hours each in 10°C steps for a total of 10 hours.

After cooling, remove from Teflon mold and size 3mm x 100mm x 1
A 00 mm resin plate was obtained.

The flame retardancy, dielectric constant, dielectric loss tangent, water absorption rate, coefficient of thermal expansion, etc. of this cured product were measured.

Example 2 Syndiotactic 1/2 polyptadiene (number average molecular weight approximately 1
20000, product name JSK-RB810 Japan Synthetic Rubber)
40g, 40g of bismaleimide described in Example 1, 2.2
20 g of -bis(4-methacryloyl 3,5-dibromophenyl)propane (manufactured by Daiichi Kogyo Seiyaku) and 5 g of dicumyl peroxide were kneaded in a roll mill at 105°C to form a homogeneous mixture.

After cooling, the mixed resin was finely ground into powder.

This was placed in a closed mold and hot press molded at 180°C for 2 hours, followed by after-curing at 200°C for 2 hours to obtain a cured resin plate measuring 3 mm x 100 mm x 100 mm.

The performance of this cured product was investigated with respect to the beating items described in Example 1.

Example 3 Syndiotactic 1/2 polybutadiene, in which 90% or more of the polymer chains are composed of 1/2 bonds (number average molecular weight approximately 120,000, trade name JSR-RB810 Japan Synthetic Rubber), 40 g, as described in Claim 2 Bismalei. 40 g of midoprepolymer, 20 g of 2,4,6 tribromo phenyl acrylate, 5 g of dicumyl peroxide, 10
Roll mill kneading was carried out at 5°C to obtain a homogeneous mixture.

After cooling, the mixed resin was finely ground into powder.

This was placed in a closed mold and hot press molded at 180°C for 2 hours, followed by after-curing at 200°C for 2 hours to obtain a cured resin plate of 3 mm x 100 mm x 100 mm.

The performance of this cured product was examined for the measurement items described in Example 1.

Example 4 Syndiotactic 1/2 polybutadiene (number average molecular weight approximately 1
20000, product name JSR-RB810 Japan Synthetic Rubber)
40 g of the bismaleimide prepolymer described in claim 4, 2,2-bis(4-methacryloyl 3
・5-Dibromophenyl)propane (manufactured by Daiichi Kogyo Seiyaku)
20g of dicumyl peroxide and 5g of dicumyl peroxide were kneaded in a roll mill at 105°C to form a homogeneous mixture.

After cooling, the mixed resin was finely ground into powder.

This was placed in a closed mold and hot press molded at 180°C for 2 hours, followed by after-curing at 200°C for 2 hours to obtain a cured resin plate measuring 3 mm x 100 mm x 100 mm.

The performance of this cured product was examined for the measurement items described in Example 1.

Comparative Example 1 40 g of 1-2 polyptadiene described in Example 2, Example 1
40 g of the described bismaleimide and 2.4 g of dicumyl peroxide were kneaded in a roll mill at 105°C to form a homogeneous mixture.

Thereafter, the same operation as described in Example 2 was carried out to obtain a cured resin plate.

The performance of this cured product was examined for the measurement items described in Example 1.

Comparative Example 2 40 g of 1,2-polybutadiene described in Example 2, 2,2-bis(4-methacryloyl 3,5-
A cured resin plate was obtained by using 40 g of (dibromophenyl) propane and 2.4 g of dicumyl peroxide in the same manner as described in Example 2.

The performance of this cured product was examined for the measurement items described in Example 1.

Measurement Results Example 5 80 g of 1,2 polybutadiene described in Example 2, 60 g of bismaleimide described in Example 1, 60 g of 2,2-bis(4-methacryloyl3-5-dibromophenyl)propane
A varnish was prepared by dissolving 10 g of dicumyl peroxide in 1000 g of tetrahydrofuran.

Glass cloth (Nittobo WE-116E-104)
) and dried at 100° C. for 10 minutes to obtain a non-tacky prepreg.

Next, stack 8 sheets of this prepreg, and place electrolytic steel foil (
A copper-clad laminate was obtained by placing a 1/2 OZ TAI treatment (manufactured by Furukawa Circuit Oil Co., Ltd.) at a temperature of 180° C. and a pressure of 40 kg/cal for an hour.

The performance of this laminate was tested in accordance with JISC-6481 in terms of electrical properties, soldering heat resistance, and trichlene resistance.

The flame retardant test was conducted under UL94. Example 6 20 g of 1-2 polybutadiene described in Example 1, 70 g of 1-2 polybutadiene described in Example 2, 60 g of bismaleimide described in Example 1, 50 g of 2-4-6 tribromo phenyl methacrylate, dicumylper Oxide 10
g was dissolved in 1000 g of tetrahydrofuran to prepare a festival.

Thereafter, the same operation as described in Example 3 was carried out to obtain a copper-clad laminate.

The performance of this laminate was examined regarding the items described in Example 3.

Comparative Example 3 80 g of 1,2 polybutadiene described in Example 2, Example 1
Listed: 80g of bismaleimide, 4g of dicumyl peroxide
．． 9 g was dissolved in 800 g of tetrahydrofuran to prepare a festival.

Thereafter, the same operation as described in Example 3 was carried out to obtain a copper-clad laminate.

The performance of this laminate was examined regarding the items described in Example 3.

Comparative Example 4 80 g of 1/2 polyptadiene described in Example 2, Example 2
A varnish was prepared by dissolving 80 g of 2,2bis(4-methacryloyl3,5-dipromophenyl)propane and 4.8 g of dicumyl peroxide in 800 g of tricrene.

Thereafter, the same operation as described in Example 3 was carried out to obtain a copper-clad laminate.

The performance of this laminate was examined regarding the items described in Example 3.

Example 7 80 g of 1,2 polybutadiene described in Example 2, 60 g of bismaleimide brevolimer described in Claim 2,
2,2bis(4-methacryloyl3,5-dibromophenyl)propane 60g, dicumyl peroxide 8g,
2g of benzoyl peroxide to 11g of tetrahydrofuran
000g to make a varnish.

Glass cloth (Nittobo WE-116E-104)
) and dried at 100° C. for 10 minutes to obtain a non-tacky prepreg.

Next, stack 8 sheets of this prepreg, and place electrolytic copper foil (
A copper-clad laminate was obtained by molding a copper-clad laminate (manufactured by Furukawa Circuit Foil Co., Ltd., 1/2 OZ TAI treatment) at a temperature of 180° C. and a pressure of 40 kg/cm for 21 hours.

The performance of this laminate was tested in accordance with JISC-6481 in terms of electrical properties, soldering heat resistance, and trichlene resistance.

The difficulty test was conducted using UL94. Example 8 20 g of 1,2 polybutadiene described in Example 1, 70 g of 1,2 polybutadiene described in Example 2, 60 g of bismaleimide prepolymer, 50 g of 2,4,6 tribromo phenyl methacrylate, 8 g of dicumyl peroxide. ,
2g of benzoyl peroxide to 11g of tetrahydrofuran
00g to make a varnish.

Thereafter, the same operation as described in Example 3 was carried out to obtain a steel clad laminate.

The performance of this laminate was examined regarding the items described in Example 3.

Measurement result

Claims (1)

[Scope of Claims] 1. A butadiene polymer containing 50% or more of 1 and 2 butadiene units having a side chain double bond in the polymer chain and a general formula [R is a divalent hydrocarbon having at least 2 carbon atoms] represents a group. ) and a 2,4,6-tripromphenol compound represented by the general formula (X is H, CH3); Curable flame retardant resin composition. 2. A butadiene polymer containing 50% or more of 1.2-butadiene units having a side chain double bond in the polymer chain, and a general formula [R represents a divalent hydrocarbon group having at least 2 carbon atoms. ] bismaleimide compound and diamine in a practical ratio of 1:1.
A bismaleimide prepolymer, which is an intermediate obtained by mixing and heating the molar ratio of a substance having a melting point of 200°C or less, and a bismaleimide prepolymer of the general formula [where X is Br or Cl and Y is H or CH3 m, n are integers of 1 to 4 (however, b is an integer of 1 to 4)] A mixture consisting of a compound represented by the following organic compound (X is H, CH3): 2, 4, 6- A thermosetting flame-retardant resin composition which is a mixture consisting of a tribromphenyl compound and a tribromphenyl compound, and which is to be thermally cured in the presence of an organic peroxide. 3. A putadiene polymer containing 50% or more of 1 and 2 putadiene units having side chain double bonds in the polymer chain and the general formula [R represents a divalent hydrocarbon group having at least 2 carbon atoms. ] A thermosetting flame retardant resin composition for thermosetting in the presence of the bismaleimide compound and a peroxide of the general formula having two acryloyl groups or methacryloyl groups in the molecule. 4 A butadiene polymer containing 50% or more of 1 and 2 butadiene units having side chain double bonds in the polymer chain and the general formula [R represents a divalent hydrocarbon group having at least 2 carbon atoms. ] and a general formula having two acryloyl or methacryloyl groups in the molecule [where X is Br or Cl, Y is H or CH3, m, n is an integer from 1 to 4, and A is -, -O-, -CO-, -SO2-, (where b is an integer of 1 to 4) ] A thermosetting mixture for thermosetting in the presence of an organic peroxide. Flame retardant resin composition.