JPS5817225B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin composition, in particular (1)
a, a polyfunctional cyanate ester having two or more cyanato groups in the molecule, the cyanate ester prepolymer,
Alternatively, a cyanato resin containing a prepolymer of the cyanate ester and an amine, b, a polyfunctional maleimide having two or more maleimide groups in the molecule, the maleimide prepolymer, or a prepolymer of the maleimide and an amine as essential components. (2) A curable resin composition obtained by mixing polypropylene, chlorinated polypropylene, or a polypropylene copolymer containing propylene as a main component and ethylene, butylene, pentene, or acrylonitrile as a copolymerization component. , is particularly needed as a resin for casting.

Conventionally, the cyanato resin of the component (1) of the present invention has been known, and is disclosed in German Patent No. 1196184 and Japanese Patent Publication No. 46-41112.
No., Special Publication No. 54-30440, Special Publication No. 52-3!27
There are No. 9 and so on.

These products have excellent heat resistance, electrical properties, and adhesion, but when used as cast products such as metal plates, they may be affected by causes such as curing shrinkage and stress generation due to differences in thermal expansion coefficients. However, it cracked and could not be used.

The inventors of the present invention investigated ways to solve these drawbacks, and found that these drawbacks could be solved by mixing polyolefins or modified polyolefins, thereby completing the present invention.

The configuration of the present invention will be explained below.

The polyfunctional cyanate ester of the (1γ-a component) of the present invention is represented by the following general formula 1, and the cyanate ester prepolymer and the prepolymer of the cyanate ester and amine are also used as the b component. It is suitably used.

R' + 0-C=N)m -... 1
[In the formula, m is an integer of 2 or more and usually 5 or less, R' is an aromatic organic group, and the cyanate ester group is bonded to the aromatic ring of the organic R] The above formula A specific example of the cyanate ester represented by is 1,3- or 1,4-dicyanatobe.

l,3,5-tricyanatobenzene, ■.

3-1■, 4-1■, 6-1■, 8-52,6- or 2,7-dicyanatonaphthalene, 1,3゜6-tricyanatonaphthalene, 4,4'-diaminobiphenyl, bis( 3-chloro-cyanatophenyl)methane, bis(4
-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3,5-dichloro-4-cyanatophenyl)furopane, 2,2-bis(3,5 -dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether, bis(4-
Cyanatophenyl, bis(4-cyanatophenyl) sulfone, tris(4-cyanatophenyl) phosphite,
These include tris(4-cyanatophenyl) phosphate and sia 1 ester obtained by reaction of novolac with cyanogen halide.

In addition to these, Tokuko Sho 41-1928, No. Sho 43-18
468, Special Publication No. 44-4791, Special Publication No. 45-1171
2, Special Publication No. 46-41112, Special Publication No. 47-26853
Cyanic acid esters described in JP-A-51-63149 and the like can also be used.

Alternatively, the polyfunctional cyanate ester described above can be polymerized in the presence of a catalyst such as a mineral acid, a Lewis acid, a salt such as carbonic acid or lithium chloride, or a phosphate ester such as tributylphosphine. It can be used as a filter prepolymer.

These prepolymers have sym-triazines, which are formed by trimerization of cyanide groups in the cyanate ester, in the general polymer.

In the present invention, it is preferable to use the prepolymer having an average molecular weight of 400 to 6,000.

Furthermore, the polyfunctional cyanate esters described above can also be used in the form of prepolymers with amines.

Examples of suitable uroamines include meta- or para-phenylene diamine, meta- or para-xylylene diamine, ■, 4- or 1,3-cyclohexane diamine, hexahydroxylylene diamine, 4,4'-diaminobiphenyl, Bis(4-amino/phenyl)methane, bis(
4-aminophenyl)ether, bis(4-aminophenyl)sulfone, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(3-chloro- 4-aminophenyl)methane, bis(4-aminophenyl)cyclohexane, 2,2-bis(4-aminophenyl)furopane, 2,
2-bis(4-amino-3-methylphenyl)propane, 2,2-bis(3,5-dibromo-14-aminophenyl)furopane, bis(4-aminophenyl)phenylmethane, 3,4-diaminophenyl -41-aminophenylmethane, 1-bis(4-aminophenyl)-
1-phenylethane and the like.

Of course, the polyfunctional cyanate esters mentioned above, their prepolymers and prepolymers with amines can be used in the form of mixtures.

(1) - Polyfunctional maleamide, which is the component (2) When used in combination with the above-mentioned component (a), a curable resin composition with even better heat resistance etc. can be obtained. This is a compound having the above.

The polyfunctional maleimide preferably used in the present invention has the following general formula [wherein R is an aromatic or alicyclic organic group with a valence of 2 or more and usually 5 or less, and Xl and V are hydrogen, chloride, etc. , or an alkyl group, n is an integer of 2 or more and usually 5 or less.

] This is a compound represented by

Maleimides represented by the above formula are maleic anhydride and 2
It can be produced by a method known per se in which maleamic acid is prepared by reacting it with an amine having at least 3 amine groups in its molecule, and then the maleamic acid is cyclodehydrated.

It is preferable that the polyvalent amines used are aromatic amines in terms of the heat resistance of the final resin, but if resin 7) flexibility and flexibility are desired, alicyclic amines may be used alone or in combination. You may.

Furthermore, it is particularly desirable that the polyvalent amines be primary amines in terms of reactivity, but secondary amines can also be used.

Suitable amines include those exemplified in C-7 for the production of prepolymers of polyfunctional Nisder cyanate and amines, melamine having a -triazine ring, and amines prepared by reacting aniline with formalin. Examples include polyamines in which benzene rings are linked with methylene bonds.

In the present invention, the polyfunctional maleimide mentioned above can be used in the form of a prepolymer instead of in the form of a so-called monomer, and furthermore, it can be used in the form of a prepolymer with the amine used in the synthesis of the polyfunctional maleimide. It can also be suitably used in the form of

Component (2) of the present invention is a polypropylene, which is a polypropylene copolymer containing polypropylene, chlorinated polypropylene, or propylene as a main component and containing ethylene, butylene, or acrylonitrile as a copolymerization component, and specifically In terms of target.

Polypropylene, chlorinated polypropylene, ethylene-7
Examples include ropine copolymer and acrylonitrile-propylene copolymer, but polypropylene containing small amounts of other copolymer components can also be used.

The number average molecular weight is 600 to 20,000, preferably 700 to 15,000, more preferably 1,000 to 500.
0.

The amount of the above polypropylene or modified polyzolopylene used is usually 1 to 80 wt%5, preferably 5% by weight in the composition.
It should be appropriately selected from the range of ~50 wt%.

The resin composition 7 of the present invention as described above is made into a heat-resistant resin by crosslinking and reticulating a cyanate ester resin composition, and the curing agent or catalyst, curing conditions, etc. are different from those of known cyanate resins. The same may be used, and of course known additives such as non-material fillers may also be used.

Examples to concretely explain the present invention with the following Examples
1 2.2-bis(4-cyana)phenyl)furopane 630
．． 57 and bis(4-manimidophenyl)ether 70
9 was preliminarily reacted at 150°C for 150 minutes, 300 g of powder of low molecular weight polypropylene (Viscol 550-p, manufactured by Seisei Kasei Co., Ltd., number average molecular weight 4000) was added, and 0.29 g of zinc octylate was added as a catalyst. Add 80
The mixture was uniformly kneaded at ℃ for 60 minutes.

The above composition was applied to a thickness of 2. Q mm length 140mm width 50
Pour into a casting mold with a steel plate of 1.5 mm.
A good cast plate was obtained by curing at 170°C for 120 minutes and 120 minutes at 170°C.

Even when this casting board was dropped onto concrete from a height of 3 m, no peeling occurred between the steel and the resin.

Comparative Example 1 A colleague made a casting plate without using the low molecular weight polypropylene in Example 1.

This temporary material cracked when it was cooled to 25° C. after hardening.

Example 2 2.2-bis(4-cyanatophenyl)propane 810
g and bis(4-maleimidophenyl)methane 90.9% were pre-reacted at 150°C for 150 minutes to form a propylene-ethynebrok copolymer with a polymer content of 7.
．． 3 wt%, molecular weight 4000) powder]
00g, add 0.2g of octyl zinc and heat to 70°C6
The mixture was kneaded for 0 minutes to obtain a uniform resin composition.

The above resin composition was coated to a thickness of 2. Omrn length 140mm,
+1] It was poured into a casting mold with a 50vrm iron plate and cured at 150°C for 1.20 minutes to obtain a good casting plate.

Even when this casting board was dropped onto concrete from a height of 3 m, no peeling occurred between the steel and the resin.

The heat softening temperature of the cured product was 19.4°C.

Comparative Example 2 A casting plate was made in the same manner as in Example 2 without using the propylene-ethylene block copolymer.

This plate developed cracks when cooled to 25°C after curing.

Example 3 2.2-bis(4-cyanatophenyl)propane 320
．． 9 and 80 g of bis(4-maleimidophenyl)methane were pre-reacted at 150°C for 100 minutes, and chlorinated polypropynone powder (20-80μ, degree of chlorination 30%,
Number average molecular weight 7000) ioo, y, zinc octylate 0
．． 3.9 was added and kneaded uniformly at 70°C.

2.0 mm thick in the casting mold. Length 1.40mm
, put an iron plate with a width of 50 mm, put the resin mixture prepared above into the casting mold, and heat it at 150'C for 120 minutes at 170°C.
A good cast plate was obtained by curing at 200°C for 60 minutes and further at 200°C for 60 minutes.

Even when this cast plate was dropped onto concrete from a height of 3 m, no peeling occurred between the iron and resin surfaces.

Moreover, the heat softening temperature of the cured product was 214°C.

Comparative Example 3 A casting plate was made in the same manner as in Example 3 without using the chlorinated polypropylene.

This plate developed cracks when cooled to 25°C after curing.

Example 4 ■, 900.9 g of 4-dicyanatobenzene and 100 g of bis(4-maleimidophenyl)methane were heated at 150°C for 10
Epicoat 828,200g to the pre-reacted for 0 minutes
, 600 g of 10-50μ powder of propylene-acrylonitrile copolymer (number average molecular weight 1700, acrylic content 15%) and activated silica 12019. Further, 0.2.9 g of tin octylate was added as a catalyst and mixed uniformly at 100°C.

This was used in the same manner as in Example 1 to obtain a casting plate containing an iron plate.

The adhesion between the iron and resin of this casting plate was extremely good. Even when dropped onto a concrete tote from a height of Om, no peeling occurred between the iron and resin surfaces.

Comparative Example 4 A casting plate was prepared under the same conditions as in Example 4 except that the propylene-acrylonitrile copolymer was not used.

This casting board had cracks and was not a good casting board.

Example 5 ■ 900 g of 4-dicyanatobenzene and 100 g of bis(4-maleimidophenyl)methane were heated at 150°C for 100 g.
Acrylic acid-modified polypropylene (acrylic acid content 3 wt%, number average molecular weight 1000
700 g of powder of 0) and 0.2.9 g of zinc octylate as a catalyst were added and mixed uniformly at 70°C.

This was used in the same manner as in Example 1 to obtain a casting plate containing an iron plate.

The adhesion between the iron and resin of this casting board was extremely good, and no peeling occurred between the iron and resin even when the casting board was dropped onto concrete from a height of 5 m.

Comparative Example 5 A casting plate was prepared under the same conditions as in Example 5 except that the glopyrene-acrylic acid copolymer was not used.

This casting board had cracks and was not a good casting board.

Claims (1)

[Scope of Claims] 1 (1) a. A polyfunctional cyanate ester having two or more cyanato groups in the molecule, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine. b. A cyanato resin containing as an essential component a polyfunctional maleimide having two or more maleimide groups in the molecule, the maleimide prepolymer, or a prepolymer of the maleimide and an amine (2) Polypropylene, chlorinated polypropylene, or propylene A curable resin composition comprising a polypropylene co-component containing as a main component and ethylene, butylene, pentene, or acrylonitrile as a copolymer component.