JPH04236228A - Production of thermosetting resin and thermosetting composition used therefor - Google Patents

Abstract

PURPOSE:To produce a thermosetting resin having excellent thermal characteristics using a solventless thermosetting resin composition having good handling properties and being liquid at ambient temperature. CONSTITUTION:(A) A polymaleimide compound such as bismaleimide is reacted with (B) a polyamino compound such as methylene dianiline and (C) maleimide based compound (e.g. allylmaleimide) having ethylenic unsaturated bond or nadic imide based compound (e.g. alylnadic imide) while heating in the presence of a radical catalyst, using the above-mentioned compound (C) at a weight ratio of 1/ 10 to 10 times based on total weight of the above-mentioned compound (A) and the compound (B) to provide the objective cured resin.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thermosetting resin and a thermosetting composition used therein. More specifically, the method for producing a thermosetting resin with excellent thermal properties using a novel thermosetting composition that is solvent-free, easy to handle, and liquid at room temperature, and the thermosetting composition described above. It is about things.

0002

[Prior Art] Generally, thermosetting products using polymaleimide compounds obtained by reacting amines and maleic anhydride have excellent heat resistance, do not generate volatile components during curing, and are different from ordinary polyimides. It has the advantage of being easier to mold.

However, when liquefying a composition containing this compound, it has a drawback that it has low solubility in common organic solvents and therefore requires a high boiling point solvent such as highly polar dimethylformamide or N-methylpyrrolidone. .

Furthermore, using only the currently known reactive diluents such as epoxy and allyl compounds has problems with the solubility and viscosity of the composition and the heat resistance of the resulting molded products. was difficult to use.

[0005]

[Problems to be Solved by the Invention] Therefore, one object of the present invention is to produce a thermosetting resin with good heat resistance using a thermosetting composition that is solvent-free and easy to handle and is liquid at room temperature. The purpose is to provide a method for manufacturing.

Another object of the present invention is to provide a thermosetting resin composition that does not emit volatile components during the thermosetting reaction process and has a low viscosity at the reaction temperature, and therefore can be advantageously used as a reaction molding resin composition. An object of the present invention is to provide a composition.

[0007]

[Means for Solving the Problems] According to the present invention, the above-mentioned first object is achieved by preparing (A) a polymaleimide compound, (B) a polyamino compound, and (C) a maleimide having an ethylenically unsaturated bond. The nadimide compound is combined with the above polymaleimide compound (A) and the above polyamino compound (
The maleimide or nadimide compound (C) having an ethylenically unsaturated bond is used at a ratio of 1/10 to 10 times the total weight of the compound and B), and the mixture is heated in the presence of a radical catalyst. This is achieved by a method for producing a thermosetting resin characterized by:

Another object of the above is to contain (A) a polymaleimide compound, (B) a polyamino compound, and (C) a maleimide or nadimide compound having an ethylenically unsaturated bond; The ratio of the maleimide or nadimide compound (C) having an ethylenically unsaturated bond to the total weight of the compound (A) and the polyamino compound (B) is within the range of 1/10 to 10 times by weight. This is achieved by a thermosetting composition characterized by the following.

The polymaleimide compound (A) used in the present invention is a divalent organic acid having a polyamino compound and a carbon-carbon double bond, and two carbonyl groups are adjacent to the double bond. It is a reaction product with

[0010] Examples of the polyamino compounds include aliphatic, alicyclic, and aromatic compounds having two or more primary amino groups in the molecule. Specifically, (a) aliphatic polyamine compounds include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, dodecamethylenediamine, neopentylenediamine, etc. ) Alicyclic polyamine compounds such as diaminocyclohexane, isophoronediamine, piperazine, 1-(2-aminoethyl)piperazine, bis(4-aminocyclohexyl)methane, bis(aminomethyl)cyclohexane, etc.
(c) As the aromatic polyamine compound, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,
3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4
'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 1,4'
-Diaminobenzophenone, 3,3'-diaminobenzophenone, bis(4-aminophenyl)triaminobenzophenone, 3,5,4'-triaminobenzanilide, melamine-1,2,4,5-tetraaminobenzene, 2 ,3,6,7-tetraaminonaphthalene, 3,3'
, 4,4'-tetraaminodiphenyl ether, 3
,3',4,4'-tetraaminodiphenylmethane,
3,5-bis(3,4'-diaminophenyl)pyridine and the following formula (I)

[0011]

[Chemical formula 1] (However, in the above formula (I), R1 has 1 to 1 carbon atoms.
Examples include compounds having three or more amino groups, such as a compound represented by an organic group of 8 and X is a number (average value) of 0.1 to 2.

[0012] In addition, 2,6- which is a heterocyclic polyamine
Diaminopyridine and 2,4,6-triaminopyridine can also be exemplified.

Among these, hexamethylene diamine,
4,4'-diaminocyclohexane, phenylenediamine, 4,4'-diaminodiphenylmethane, methylphosphine, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, diaminonaphthalene, 4,4 '-diaminodiphenyl sulfide, 2,4-diaminotoluene, 2,
6-diaminotoluene, 2,2-bis(4-aminophenyl)propane, 1,2-dianilinoethane, diethyldiaminotoluene, 3,4'-diaminobenzanilide, bis(aminophenyl)-1,3,4-oxa Dithiazole, 2,2'-bis(m-aminophenyl)-
5,5'-dibenzimidazole, N,N'-bis(p-aminobenzoyl)-4,4'-diaminodiphenylmethane, benzidine, 1,2,4-triaminobenzene, 1,3,5-triamino benzene, 2,4,6
-triaminotoluene, 2,4,6-triamino-1,
3,5-trimethylbenzene, 1,3,7-triaminonaphthalene, 2,4,4'-triaminodiphenyl,
2,4,4'-triaminodiphenylmethane, p-aminophenyl-4,4'-diphenylmethane, tri(
4-aminophenyl)methane, 2,4,4'-3,4
'-Diamino diphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 4
, 4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, m-xylylenediamine, p-xylylenediamine, tolylenediamine and the above formula (I) An aniline-formalin condensate represented by is preferably used. The above polyamine compounds can be used alone or in combination of two or more.

Polymaleimide compound (A
), which is a divalent organic group having a carbon-carbon double bond and in which two carbonyl groups are adjacent to the double bond, is a compound represented by the following formula (II). maleic anhydride derivative and/or 3,4,5
, 6-tetrahydrophthalic anhydride derivatives.

[0015]

[Chemical formula 2] (However, in the above formula (II), R2 and R3 are
They are the same or different and represent a hydrogen atom and/or an aliphatic, alicyclic, or aromatic hydrocarbon group having 10 or less carbon atoms. )
Specifically, maleic anhydride, citraconic anhydride, ethyl maleic anhydride, dimethyl maleic anhydride, phenyl maleic anhydride, cyclohexanyl maleic anhydride, 3,4,5,6-tetrahydro anhydride. phthalic acid,
Examples include methyl-3,4,5,6-tetrahydrophthalic anhydride. Among these, maleic anhydride or its derivatives are preferred, and maleic anhydride is particularly preferred.

2 having a carbon-carbon double bond as described above
One type or two or more types of the compound which is a valent organic group and has two carbonyl groups adjacent to the double bond can be used.

The polymaleimide compound (A) used in the present invention is a divalent organic acid having the above polyamine and a carbon-carbon double bond, and two carbonyl groups are adjacent to the double bond. It is a reaction product obtained by reacting with and by a conventional method.

On the other hand, as the polyamino compound (B) used in the present invention, the compounds listed above as raw materials for the polymaleimide can be used. These can be used alone or in combination of two or more.

The blending ratio of the polymaleimide compound (A) and the polyamino compound (B) is such that the active hydrogen equivalent of the maleimide group of component (A) and the amino group of component (B) is 1/10 to 2;
Preferably 1/9 to 1.5, more preferably 1/8 to 1.5
Used in the range 1.

[0020] Preliminary reaction of the polymaleimide compound (A) and the polyamino compound (B) under heating can also be preferably carried out for liquefaction.

[0021] Preliminary reaction conditions are preferably carried out at a temperature of 50 to 180°C for 5 minutes to 5 hours while stirring or kneading. In this preliminary reaction, the amino groups of the polyamino compound (B) cause Michael addition to the unsaturated bonds of the polymaleimide compound (A), but as more than 5% of the unsaturated bonds of all the maleimide groups react, the polymaleimide It is possible to reduce the crystallinity of the compound and make it easier to liquefy.

Further, as the maleimide or nadimide compound (C) having an ethylenically unsaturated bond used in the present invention, the following formula (III) and/or (IV
) is used.

[0023]

embedded image (However, in the above formula (III), R is a group having an ethylenically unsaturated bond. Also, R4, R5
are the same or different, and have a hydrogen atom and/or a carbon number of 10
Represents the following aliphatic, alicyclic, aromatic, and aromatic hydrocarbon groups. )

[0024]

embedded image (However, in the above formula (IV), the definition of R' is the same as R in the above formula (III). Also, R6, R
7 is the same or different and represents a hydrogen atom and/or an aliphatic, alicyclic, aromatic, or aromatic hydrocarbon group having 10 or less carbon atoms. ) In each of the above formulas, R and R' are preferably allyl, metaallyl, propargyl, allyloxy, or metaallyloxy groups.

[0025] The maleimide or nadimide compound (C) having an ethylenically unsaturated bond has an imide skeleton in the molecule and has excellent heat resistance. Since it significantly improves solubility, it is suitably used for the purpose of liquefaction.

The ratio of the above component (C) to be used is as follows: the above polymaleimide compound (A), the above polyamino compound (
Based on the total weight of B), the amount is 1/10 to 10 times, preferably 1/9 to 5 times, and more preferably 1/7 to 1 times.

If the above-mentioned (C) component deviates from the above-mentioned usage ratio, the solubility of the above-mentioned (A) component will be significantly lowered, causing undesirable results in liquefaction such as the formation of precipitates at room temperature, and physical properties may deteriorate. This is undesirable as it causes a decrease in the surface area.

In the present invention, the above (A), (B), (
In addition to component C), compounds that can react with each of the above components may be used.

For example, an ethylenically unsaturated compound that can undergo a radical reaction with the unsaturated bond of the component (A) or the unsaturated bond of the component (C), and can undergo a Michael addition with the amino group of the component (B), is It can be preferably used for the purpose of lowering the viscosity of the system and improving its handling properties, for the purpose of liquefaction, and for the purpose of improving the physical properties of the obtained molded product. Specifically, such ethylenically unsaturated compounds include styrene, α
-Methylstyrene, (meth)acrylic acid, glycidyl methacrylate, dially(iso,tere)phthalate, tri(meth)allyl(iso)cyanurate, trivinyl(
Examples include iso)cyanurate and triallyl trimellitate.

[0030] These ethylenically unsaturated compounds can be used singly or in combination of two or more, and the proportion used is per 100 parts by weight of the above components (A), (B), and (C).
Preferably it is 100 parts by weight or less.

The ethylenically unsaturated compound is the polymaleimide compound (A) and the polyamine compound (B).
If necessary, it may be added during the preliminary reaction for the purpose of liquefaction.

[0032] Epoxy compounds that can react with the above component (B) can also be preferably used from the viewpoint of improving handleability and physical properties. Specifically, such epoxy compounds include 4,4'
-Methylene diphenol, bisphenol A, polyglycidyl ether compounds of polyphenols which are condensates of phenols and α- and /or β-naphthol with formaldehyde, glyoxal, terephthalaldehyde, p-hydroxybenzaldehyde, etc., terephthalic acid, isophthalic acid , polyglycidyl ester compounds of polycarboxylic acids such as trimellitic acid, polyaminoglycidyl compounds of the above polyamines, p-hydroxybenzoic acid, oxynaphthoic acid, phenols, α- and / or β-naphthol, p-formylbenzoic acid, etc. polyglycidyl ether ester compounds of polyhydroxycarboxylic acids which are condensates of
-methyl)glycidyl cyanurate is an example.

The proportion of these epoxy compounds used is per 100 parts by weight of the above components (A), (B), and (C).
Preferably it is 100 parts by weight or less.

The thermosetting composition used in the present invention further contains a radical catalyst in addition to the above (A), (B), and (C) and an ethylenically unsaturated compound and an epoxy compound added as necessary. contains.

As the radical catalyst used in the present invention, organic peroxides and organic azo compounds are preferably used. Specifically, the organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl isobutal ketone peroxide; cumene hydroperoxide;
Hydroperoxides such as tert-butyl hydroperoxide; peroxy esters such as tert-butyl peroxyoctoate, tert-butyl peroxybenzoate, etc.; 1,3-bis(tert-butyl peroxyisopropyl)benzene, Dialkyl peroxides such as mil peroxide, tris(tert-butyl peroxy) triazine, etc.; diacyl peroxides such as isobutyryl peroxide, lauroyl peroxide, benzoyl peroxide, etc.; 1,1-di-tert-butyl peroxide -3,3,5-trimethylcyclohexane, 1,1
- di-tert-butyl peroxycyclohexane,
Peroxy ketals such as 2,2-di-(tert-butylperoxy)-butane; tert-butyl peroxyisopropyl carbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl Percarbonates such as peroxydicarbonate and the like can be mentioned. Further, specific examples of the organic azo compound include azobisalkanonitriles such as azobisisobutyronitrile and azobiscarbonamide.

These radical catalysts may be used alone or in combination of two or more. The amount of these radical catalysts to be used is preferably 0.05 to 15% by weight based on the total amount of component (A), component (B), component (C) and the ethylenically unsaturated compound added as necessary. is 0
．． The amount is about 1 to 10% by weight, particularly preferably about 0.2 to 5% by weight.

[0037] The above radical catalyst is added with an organic acid salt of a polyvalent metal such as an octylate or a naphthenate of cobalt, manganese, iron, copper, or other heavy metals, and if necessary, a salt such as dimethylaniline, dimethyl para-toluidine, etc. Polymerization accelerators such as tertiary amines, hydroquinone, naphthoquinone, tert-butylcatechol, p-benzoquinone,
It is also preferable to add a small amount of a polymerization inhibitor such as butylated hydroxytoluene or nitroxide radicals in order to control the reaction rate and improve the pot life.

In the present invention, in addition to the above-mentioned radical catalyst, other catalysts may be used in combination as necessary. For example, when the reaction system contains an epoxy group, it is preferable to add an epoxy curing agent such as imidazoles, tertiary amines, hydrazils, etc. from the viewpoint of controlling the reaction rate and improving physical properties.

[0039] The liquid thermosetting resin composition of the present invention can be molded as it is or by adding a thickener and the like in various ways to form useful resin molded products.

The reaction method for producing a cured resin molded article from the composition of the present invention is to mix the above-mentioned components, perform, for example, dry blending, slurry blending or melt blending, and then injecting the blend into a mold. A heating reaction method is useful.

The reaction temperature depends on the components (A) and (B) used.
It varies depending on the ingredients, the type of component (C) and other compounds and radical catalysts added as necessary, and their usage ratio, etc.
Preferably 50-300°C, more preferably 60-28°C
The temperature is 0°C, particularly preferably about 70 to 250°C.

[0042] The reaction time may be sufficient as long as it is sufficient to harden the desired resin, and this time varies depending on the type of raw materials used, the proportion used, the reaction temperature, etc.
Preferably 10 seconds to 200 minutes, more preferably 20 seconds to
It is about 150 minutes, particularly preferably about 30 seconds to 100 minutes.

[0043] The reaction can be carried out at normal pressure to increased pressure, but
At this time, to prevent water from entering the atmosphere and oxidation deterioration of the resin,
It is preferable to carry out under an inert gas atmosphere such as nitrogen or argon.

[0044] It is also preferable to improve the physical properties by heat-treating the reaction molded product at a temperature higher than the reaction temperature, if necessary.

The thermosetting resin composition of the present invention may optionally contain a thermoplastic polymer, a filler, a low shrinkage agent such as a bicyclo compound, a spiro compound, a pigment, a coloring agent, an oxidation stabilizer, and an ultraviolet ray. An absorbent, a mold release agent, etc. can be contained.

It is also possible to obtain a composite material with good physical properties by molding and curing the above-mentioned curable resin composition in the presence of a fibrous reinforcing material such as aramid fiber, carbon fiber or glass fiber.

[0047]

Effects of the Invention The thermosetting resin composition of the present invention is liquid even at a temperature near room temperature, has a low viscosity near the molding temperature, and is excellent in handleability.

Furthermore, the resin molded product obtained by curing this resin has good heat resistance and extremely excellent mechanical properties such as no cracking even in a system without the addition of a reinforcing material.

[0049]

[Examples] The present invention will be described in detail below with reference to Examples.
The examples are for illustrative purposes only, and the invention is not limited thereto. In addition, "parts" in the examples are "parts by weight"
The heat distortion temperature is the value measured by HDT of a molded plate heat-treated at 200° C. for 5 hours.

[0050]

[Example 1] 41 parts of N,N'-methylene-di-p-phenylenebismaleimide, 9 parts of 4,4'-methylene dianiline, and 50 parts of allylmaleimide are mixed for 10 minutes in an oil bath at 130°C. A homogeneous liquid mixture was obtained.

[0051] Three parts of "Perkadox 14" (manufactured by Kayaku Nouri Co., Ltd.) consisting of 1,3-bis(tert-butylperoxyisopropyl)benzene was uniformly dissolved in this, and the mixture was preheated to 150°C. Pour into the mold 30
Allowed to cure for minutes.

[0052] The molded plate after heat treatment is blackish brown, and its HDT
is 225℃, Izod impact strength is 2.7kgcm/c
m2, and it was found that the molded plate had excellent heat resistance and toughness.

[0053]

[Example 2] 41 parts of N,N'-methylene-di-p-phenylene bismaleimide, 9 parts of 4,4'-methylene dianiline, 29 parts of triallylisocyanurate, and 14 parts of allylnadimide were mixed in oil at 130°C. The mixture was mixed in a bath for 10 minutes, and 7 parts of glycidyl methacrylate was added thereto to obtain a homogeneous liquid mixture. The viscosity of this resin composition at 50° C. was measured by a falling ball viscosity method and was found to be 8 ps.

After uniformly dissolving 3 parts of "Parkadox 14" and 0.5 part of imidazole in this, the solution was placed in a mold preheated to 150° C. and cured for 30 minutes.

[0055] The molded plate after heat treatment is blackish brown and has an HDT of 2.
94℃, Izod impact strength is 3.8kgcm/cm2
It was found that it has excellent heat resistance and toughness.

[0056]

[Example 3] 41 parts of N,N'-methylene-di-p-phenylenebismaleimide, 9 parts of 4,4'-methylene dianiline, 21 parts of triallyl isocyanurate, and 21 parts of allylnadimide were mixed in oil at 130°C. The mixture was mixed in a bath for 10 minutes, and 7 parts of glycidyl methacrylate was added thereto to obtain a homogeneous liquid mixture.

After 3 parts of "Parkadox 14" and 0.5 part of imidazole were uniformly dissolved in this, the solution was placed in a mold preheated to 150° C. and cured for 30 minutes.

[0058] The molded plate after heat treatment is blackish brown and has an HDT of 2.
67℃, Izod impact strength is 1.5kgcm/cm2
It was found that it has excellent heat resistance and toughness.

[0059]

[Example 4] 41 parts of N,N'-methylene-di-p-phenylenebismaleimide, 9 parts of 4,4'-methylene dianiline, 29 parts of triallylisocyanurate, and 14 parts of allylmaleimide were mixed in an oil bath at 130°C. The mixture was mixed for 10 minutes, and then 7 parts of glycidyl methacrylate was added thereto to obtain a homogeneous liquid mixture.

After 3 parts of "Parkadox 14" and 0.5 part of imidazole were uniformly dissolved in this, the solution was placed in a mold preheated to 150° C. and cured for 30 minutes.

[0061] The molded plate after heat treatment is blackish brown and has an HDT of 3.
00℃ or higher, Izod impact strength is 1.4kgcm/c
m2, it was found to be excellent in heat resistance and toughness.

[0062]

[Example 5] 41 parts of N,N'-methylene-di-p-phenylene bismaleimide, 9 parts of 2,4'-tolylene diamine, 29 parts of triallyl isocyanurate, and 14 parts of allylnadimide were mixed in oil at 130°C. The mixture was mixed in a bath for 10 minutes, and 7 parts of glycidyl methacrylate was added thereto to obtain a homogeneous liquid mixture.

After 3 parts of "Parkadox 14" and 0.5 part of imidazole were uniformly dissolved in this, the solution was placed in a mold preheated to 150° C. and cured for 30 minutes.

[0064] The molded plate after heat treatment is blackish brown and has an HDT of 2.
94℃, Izod impact strength is 3.0kgcm/cm2
It was found that it has excellent heat resistance and toughness.

[0065]

[Example 6] 41 parts of N,N'-methylene-di-p-phenylenebismaleimide, 9 parts of a polyamino compound represented by the following formula (V), and 2 parts of triallylisocyanurate
9 parts of allylnadimide and 14 parts of allylnadimide were added in an oil bath at 130°C.
After mixing for 0 minutes, 7 parts of glycidyl methacrylate was added to obtain a homogeneous liquid mixture.

[0066]

embedded image (X=1.7 in the above formula (V)) The viscosity of this resin composition at 50° C. was measured by a falling ball viscosity method and found to be 8 ps.

After 3 parts of "Parkadox 14" and 0.5 part of imidazole were uniformly dissolved in this, the solution was placed in a mold preheated to 150° C. and cured for 30 minutes.

[0068] The molded plate after heat treatment is blackish brown and has an HDT of 2.
94℃, Izod impact strength is 2.0kgcm/cm2
It was found that it has excellent heat resistance and toughness.

Claims (2)

[Claims] Claim 1: (A) a polymaleimide compound, (B) a polyamino compound, and (C) a maleimide or nadimide compound having an ethylenically unsaturated bond;
The above-mentioned maleimide or nadimide compound (C) having an ethylenically unsaturated bond is used at a ratio of 1/10 to 10 times the total weight of the compound, and the mixture is heated in the presence of a radical catalyst. Characteristic manufacturing method of thermosetting resin. 2. Contains (A) a polymaleimide compound, (B) a polyamino compound, and (C) a maleimide or nadimide compound having an ethylenically unsaturated bond, and the polymaleimide compound (A) and the polyamino compound ( The maleimide or nadimide compound having the above ethylenically unsaturated bond (C
) is 1/10 to 10 times by weight.