JPH0320329A - Production of thermosetting resin, composition and resin - Google Patents

Abstract

PURPOSE:To produce a thermosetting resin excellent in heat resistance, chemical resistance and mechanical properties within a short time by reacting a specified polycycloimino ether by heating with a specified low molecular ethylenically unsaturated compound and a specified ethylenically unsaturated monomer in the presence of a specified mixed catalyst. CONSTITUTION:A thermosetting resin is produced by reacting by heating a polycycloimino ether (A) of formula l (wherein (n) is 2-4; R is an n-valent hydro carbon residue which may be interrupted or substituted by a group containing an atom other than a carbon atom; Z is a direct bond or a group of formula Il; and Ra-Rd are each H, CR3, C2H5, C3R7, a phenyl, a tolyl or a benzyl provided that R may be a direct bond when (n)=2, with a low molecular ethylenically unsaturated compound (B) containing a functional group reactive with the cycloimino ether group of component A and an ethylenically unsaturated bond, and an ethylenically unsaturated monomer (C) having an ethylenically unsaturat ed bond but not having any functional group reactive with the cycloimino ether group of component A in such amounts that 10-400 pts.wt. component C is used per 100 pts.wt. total of components A and B in the presence of both an acid catalyst and a radical catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Field of Application The present invention relates to a method for producing thermosetting resins. More specifically, the present invention relates to a method for producing a thermosetting resin having excellent heat resistance, chemical resistance, and 1a mechanical properties at a high curing rate and with excellent moldability.

(b) Prior Art In recent years, with the advancement of technology, resins with excellent heat resistance, mechanical properties, and moldability have been required. Among these resins, reactive polymerization type resins using reactive monomers or oligomers, that is, resins in which polymerization and polymerization are simultaneously performed using relatively low viscosity raw materials, are attracting particular attention. Known examples of such resins include polyurethane resins, polyurea resins, nylon resins, epoxy resins, and unsaturated polyester resins, some of which are commercially available.

However, each of these resins has its advantages and disadvantages.
For example, polyurethane resins have low ripening resistance, and unsaturated polyester resins have drawbacks such as the time required for reaction, that is, molding, and cannot necessarily be said to have sufficient performance and shapeability.

On the other hand, thermosetting resins using oxazolines as one of the monomers and reactions between oxazolines are known from the following literature.

JP-A-59-1533 discloses that a bis(2-oxazoline) compound and a dicarboxylic acid are reacted by heating in the presence of a phosphite using an equimolar or smaller proportion of the dicarboxylic acid, A method of making a thermoset resin is disclosed.

JP-A-63-146924 discloses a copolymerization reaction of oxazoline and a bis- or polyphenolic compound by heating to a temperature of 100 to 200°C in the presence of an alkali or alkaline earth metal cation complex catalyst. let me,
A method of making poly(ether amide) is disclosed.

Japanese Patent Publication No. 61-57330 discloses a method for producing an unsaturated polyester modified with oxazoline by reacting an oxazoline derivative having 1 to 4 oxazoline rings in the molecule with an unsaturated polyester having a carboxyl group. has been done. According to the publication, the reaction is 1
The process is carried out at a temperature of 00 to 250°C for about 10 minutes to 3 hours.

JP-A-64-48811 discloses an organic compound having a 2-oxazoline ring and a boiling point of 140°C or higher;
A curable unsaturated polyester resin composition containing an unsaturated polyester resin, a reinforcing fiber such as glass fiber, and a polymerization initiator (peroxide) is disclosed.

However, generally speaking, the above-mentioned thermosetting resins have high handling temperatures and high forming temperatures, and cannot necessarily be said to have sufficient moldability.

(Object of the invention) Therefore, an object of the present invention is to provide a novel method for producing thermosetting resins.

Another object of the present invention is to provide novel compositions, namely polycyclic iminoethers, ethylenically unsaturated compounds reactive with iminoether groups, mixtures of ethylenically unsaturated monomers unreactive with iminoether groups or carboxyl groups. It is an object of the present invention to provide a method for producing a thermosetting resin using a mixture further containing a compound having a group reactive with an iminoether group but having no ethylenically unsaturated bond.

Another object of the present invention is to achieve a heat curing reaction in a very short time, which is therefore very industrially advantageous.
An object of the present invention is to provide a method for producing a thermosetting resin.

Still another object of the present invention is to provide a mature hardening 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 method for producing a thermosetting resin using a thermosetting resin.

Still another object of the present invention is to provide a thermosetting resin with excellent heat resistance, mechanical properties, and chemical resistance.

Still another object of the present invention is to provide a thermosetting resin that is excellent as a composite material by curing a thermosetting composition containing a fibrous filler.

Further objects and advantages of the present invention will become apparent from the description below.

(d) Structure of the Invention According to the present invention, such objects and advantages of the present invention are as follows: fA) The following formula (I) The polycyclic imino ether represented by the above formula (I> used in the method of the present invention) According to the definition, when 2 is a direct bond, (A) is a polycyclic imino ether represented by the following formula (I) -1, (B) a functional group that can react with the cyclic imino ether group of the above polycyclic imino ether. and (C) a low molecular weight ethylenically unsaturated compound having an ethylenically unsaturated bond, and (C) having an ethylenically unsaturated bond but not having a functional group that can react with the cyclic imino ether group of the polycyclic imino ether. Acidic It is characterized by carrying out a heating reaction in the coexistence of a catalyst and a radical catalyst.It is achieved by the method for producing thermosetting resins.

and Z represents oxazines.

In the above formula <■> (including formulas (I>-1 and (I)-2), R is an n-valent hydrocarbon residue.

The hydrocarbon residues may be interrupted or substituted with atoms other than carbon atoms or groups containing atoms other than carbon atoms. n is an integer from 2 to 4. Therefore, n-monovalent hydrocarbon residues are divalent, trivalent or tetravalent hydrocarbon residues. However, when n is 2, R can represent a direct bond.

The hydrocarbon residue may be, for example, aliphatic, alicyclic, or aromatic. Preferably carbon number is 1
to 10 aliphatic groups, alicyclic groups having 5 to 10 carbon atoms, or aromatic groups having 6 to 12 carbon atoms.

As the hydrocarbon residue, when n=2, for example, an alkylene group having 1 to 10 carbon atoms such as methylene, ethylene, trimethylene, 1,2-brobylene, tetramethylene, hexamethylene, neobenzene, decamethylene; cyclohexylene, - Divalent alicyclic groups having 5 to 10 carbon atoms such as eo: Divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms such as p-phenylene, m-phenylene, naphthylene, and biphenylene are preferred. I can do it. Similarly, when n=3, for example, -Cl2-CH-C}12- can be mentioned as a preferable example.

Further, as a case where n=4, for example, it is preferable to cite the case where n=4.

Hydrocarbon residues such as those mentioned above may be interrupted by atoms other than carbon atoms, such as oxygen atoms, sulfur atoms or one NRg-. Rg is a hydrogen atom or a monovalent hydrocarbon such as an alkyl group.

Furthermore, the above hydrocarbon residues may be substituted with groups containing atoms other than carbon atoms.

Such substituents include, for example, chloro, bromo, nitro, methoxy, cyano. These include amide, acetamide, etc.

Moreover, in the above formula (I), Ra, Rb, Re,
Rd, Re and Rf are the same or different and are a hydrogen atom, methyl, ethyl, proyl, phenyl, tolyl or benzyl. Among these, hydrogen atoms or methyl are preferable, and it is particularly preferable that all of them are hydrogen atoms, or one of them is methyl and all of the others are hydrogen atoms.

Examples of the polycyclic iminoether of formula (I) include the following compounds.

Examples of oxazolines of formula (I>-1;2,2'-bis(
2-oxazoline), 2.2'-monoethylenebis(2-oxazoline), 2.2'-tetramethylenebis(2-oxazoline). 2.2'-1-hexamethylenebis(2-oxazoline>.2.2'-octamethylenebis(2-oxazoline), 2.2'-1.4-cyclohexylenebis(2-oxazoline).2.2 '-bis(4-methyl-2-oxazoline).2.2'-bis(5-methyl-2-oxazoline),2.2'1m-phenylenebis(2-oxazoline),2.2'p- Phenylenebis(2-oxazoline), 2.2'-m-phenylenebis(4-methyl-2-oxazoline), 2.2'-m-phenylenebis(5-methyl-2-oxazoline), 2.
2'-p-phenylenebis(4-methyl-2-oxazoline), 2'-p-phenylenebis(5-methyl-
2-oxazoline), 1,3.5-}lis(2-oxazolinyl-2)benzene, etc.

Among these, 2,2'-bis(2-oxazoline), 2
, 2'-tetramethylenebis(2-oxazoline), 2
．． 2'-m-phelenebis(2-oxazoline), 2. 2'-p-phenylenebis(2-oxazoline) is preferred.

Examples of oxazines of formula (I>-2.2.2'-bis(5
, 6-dihydro-48-1,3-oxazine), 2.2
'-ethylenebis(5,6-dihydro-48-1.3-
oxazine), 2,2'-tetramethylenebis(5,6
-dihydro-48-1,3-oxazine>,2,2'-hexamethylenebis(5,6-dihydro-48-1.
3-oxazine), 2,2'-octamethylenebis(5
, 6-dihydro-4H-1,3-oxazine>, 2.
2'-1,4-cyclohexylenebis(5,6-dihydro-48-1,3-oxazine),2,2'-bis(4
-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-bis(5-methyl-5,6-dihydro-48-1,3-oxazine), 2,2'-bis( 6-
methyl-5,6-dihydro-48-1,3-oxazine), 2,2'-m-phenylenebis(5,6-dihydro-4H-1,3-oxazine). 2.2'-p-phenylenebis(5,6-dihydro-48-1,3-oxazine). 2.2'-m-phenylenebis(4-methyl-5
, 6-dihydro-4H-1,3-oxazine), 2.2
'-m-phenylenebis(5-methyl-56-dihydro-4H-1.3-oxazine), 2.2'-m-
Phenylenebis(6-methyl-5.6-dihydro-48
-1.3-oxazine)+2+2'-P-phenylenebis(4-methyl-5.6-dihydro-48-1.3-oxazine), 2.2'-p-phenylenebis(5-methyl-5.6 -dihydro48-1.3-oxazine>.
2.2'-p-phenylenebis(6-methyl-5,6-
dihydro-4H-1,3-oxazine> etc.

Among these, 2,2'-bis(5,6-dihydro-4H
-1,3-oxazine), 2,2'-tetramethylenebis(5,6-dihydro-48-1,3-oxazine),
2.2'-m-phenylenebis(5,6-dihydro-4
8-1. 3-oxazine). 2,2'-p-phenylenebis(5,6-dihydro 4H-1,3-oxazine) is preferred.

In the present invention, one kind or two or more kinds of polycyclic iminoethers can be used in combination. When using one or more kinds in combination, oxazolines, oxazines, or oxazolines and oxazines can be used.

Component (B) used in the present invention is an ethylenically unsaturated compound having at least one ethylenically unsaturated bond and a functional group capable of reacting with the cyclic iminoether group of the polycyclic iminoether in its molecule.

Here, the functional group capable of reacting with the cyclic imino ether group of the polycyclic imino ether is preferably a carboxyl group, hydroxy group, amino group, epoxy group, or intramolecular carboxylic acid anhydride group.

Preferred examples of the component (B) include low-molecular compounds having ethylenically unsaturated bonds, such as organic polycarboxylic acids or intramolecular acid anhydrides, organic polyhydroxy compounds, organic polyamino compounds, and organic polyeboxy compounds. be able to.

(B) The ethylenically unsaturated bond possessed by the moiety is preferably a carbon-carbon double bond adjacent to a carbonyl group, for example.

Examples of the organic polycarboxylic acid or its intramolecular acid anhydride include maleic acid, halogenated maleic acid, fumaric acid, citraconic acid, itaconic acid, halogenated itaconic acid, 5-norbornene-2,3-dicarboxylic acid, Examples include methyl-5-norbornene-2,3-dicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, tetrachlorophthalic acid, and intramolecular acid anhydrides thereof.

Moreover, as an organic polyhydroxy compound, for example, 2-
aliphatic hydroxy compounds such as butene-1,4-diol, 2-hydroxyethyl fumarate and 3,3'
-Diallyl bisphenol A, allyl bisphenol A
, bis(3-aryl-4-hydroxyphenyl)methane, and aromatic hydroxy compounds such as 3-aryl-4-hydroxyphenyl-P-hydroxytoluene.

As the organic polyamino compound, for example, aromatic amines and amines having a methylamino group bonded to an aromatic ring are preferred, and examples thereof include 2,4-diaminostyrene.

Further, examples of the organic polyepoxy compound include glycidyl esters of carboxylic acids containing ethylenically unsaturated bonds as described above, glycidyl ethers of hydroxy compounds containing ethylenically unsaturated bonds, and the like. Examples include fumaric acid diglycidyl ester, maleic acid diglycidyl ester, and diglycidyl ether of 3,3'-diallylbisphenol A.

In addition to the above-mentioned compounds, component (B) may also include compounds having only one functional group reactive with an iminoether group in the molecule, such as 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate. , 2-aminoethyl methacrylamide, and glycidyl methacrylate.

The above-mentioned low molecular weight compounds can be used alone or in combination of two or more.

Such low molecular weight compounds are used in an equivalent ratio of polycyclic imino ether to low molecular weight compound of 10:1 to 1:5, more preferably 5:1 to 1:1.

The component (C) used in the present invention is an ethylenically unsaturated monomer that has an ethylenically unsaturated bond but does not have a functional group that can react with the polycyclic imino ether group of the polycyclic imino ether. be.

As component (e), for example, styrenes represented by the following formula, (meth)acrylic esters represented by the following formula, vinyl acetate, aromatic polycarboxylic acid allyl ester, or triallyl(iso)cyanurate are preferably used. Ru.

Examples of the above-mentioned styrenes include styrene, α-methylstyrene, t-butylstyrene, chlorostyrene, vinyltoluene, divinylbenzene, and the like.

Further, as the acrylic ester or methacrylic ester of the above formula, for example, an ester of acrylic acid or methacrylic acid with an aliphatic alcohol such as methyl alcohol, ethyl alcohol, proyl alcohol, octyl alcohol, hexanol, tetrahydrofurfuryl alcohol, etc. can be mentioned.

Examples of the aromatic polycarboxylic acid allyl ester include diallyl phthalate and diallyl isophthalate.

Component (C) can be used alone or in combination of two or more. Styrene is particularly preferably used as component (C).

In the present invention, the above (A) polycyclic imino ether, the above (B) ethylenically unsaturated compound, and the above (e)
The ethylenically unsaturated monomer (C) is used in an amount of 10 to 400 parts by weight per 100 parts by weight of the +A>component and component (B). If the above range is exceeded, the viscosity of the resin composition may become high, causing difficulty in forming the composition, the reactivity of the composition may decrease, requiring high temperatures for reaction, or the physical properties of the obtained composition may not be sufficient. I don't want it to disappear. In addition, the preferred usage ratio is based on the same criteria as above, with component (C) being 2
The amount of component (C) is 0 to 300 parts by weight, and a more suitable proportion is 25 to 250 parts by weight of component (C) based on the same criteria as above.

The thermosetting compound used in the present invention further contains an acidic catalyst and a radical catalyst in addition to the above-mentioned components (Al, (Bl) and (Cl).

Acidic catalysts are used for ring-opening polymerization of polycyclic imino ethers and polycyclic imino ethers and ethylenically unsaturated compounds (B).
The radical catalyst also contributes to the reaction with the ethylenically unsaturated compound (B) and the ethylenically unsaturated monomer (e
) is believed to contribute to the cleavage of ethylenically unsaturated double bonds.

As the acidic catalyst used in the present invention, the following compound group can be exemplified.

(i) A protic acid with a pKa of 2.5 or less, (fl
Esters of protic acids with pK a of 1.0 or less, (
in) Nofrotonic acid monosalt with pKa of 2.5 or less, 0■
Lewis acid and its complex, M alkyl halide, (l/8 iodine, (4) following formula <IF)? Halogen phenols represented by ■ Halogenophthalic acids represented by the following formula (In>) and/or halogenophthalic anhydride represented by the following formula (IV). pKa is 2.5
The following protic acids (11 are preferably organic sulfonic acids, phosphonic acids or inorganic acids, such as trifluoromethanesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid) Phosphonic acids such as phenylphosphonic acid; Inorganic acids such as sulfuric acid, phosphoric acid, phosphorous acid, phosphinic acid and perchloric acid.

As the protic acid ester (ii) having a pKa of 1.0 or less, organic sulfonic acid esters and inorganic protic acid esters are preferred. As the alcohol component forming the ester, aliphatic alcohols having 1 to 10 carbon atoms are preferably used. Examples of the ester include methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, methyl benzenesulfonate, ethyl benzenesulfonate, methyl P-}luenesulfonate,
Sulfonic acid esters such as ethyl p-toluenesulfonate and ethyl trifluoromethanesulfonate: Examples include esters of inorganic protonic acids such as dimethyl sulfate and diethyl sulfate.

Salts of protonic acids with a pKa of 2.5 or less (as il,
Salts of the above-mentioned protic acids (il, hexamethylene diamine, piperazine, m-xylylene diamine, 4.4'-
Diaminodiphenylmethane, pyridine, 2.2'-m-
Salts of organic amine compounds such as phenylenebis(2-oxazoline), trifluoromethanesulfonic acid, and the like are preferably used.

Lewis acids and their complexes (M is, for example, Lewis acids such as titanium tetrachloride, tin tetrachloride, zinc chloride, aluminum chloride, boron trifluoride; or complexes of these Lewis acids with ethers or phenols, such as trifluoride; Preferred examples include boron ether complexes.

As the alkyl halide M, alkyl iodide or alkyl bromide is particularly preferred. Further, the number of carbon atoms in the alkyl group is preferably 1 to 10, and the alkyl group may be substituted with phenyl. As alkyl halide M,
For example, methyl iodide, ethyl iodide, probyl iodide,
Preferred examples include butyl iodide, benzyl iodide, and benzyl bromide. Iodine M is simple iodine.

Halogenophenols represented by the above formula (II) are also suitable catalysts.

In the above formula (II>), X1 and X2 are the same or different and are halogen atoms. As the halogen atoms, for example, chlorine atoms and bromine atoms are particularly preferable.
is a number of 0.1 or 2.

Preferably, m is 1. Also, in that case (m=1)
It is particularly preferable that X2 is bonded to the ortho position with respect to the hydroxyl group in formula (II).

Y is -SO2R1, -COR2. -CN or -N
It is O2.

The above formula (I[) can be represented by the following formulas depending on the definition of Y.

(X2)m (X2)m (X2)m In the above formula (If)-1, the alkyl having 1 to 20 carbon atoms in R1 may be linear or branched.
Alkyl having 1 to 10 carbon atoms is preferred. Such alkyls include, for example, methyl, ethyl, n-propyl, i
so-propyl, n-butyl, igo-butyl, g
ee-butyl, tert-butyl, n-pentyl, n
-hexyl, n-hebutyl, n-octyl, n-nonyl, n-decyl. Examples include n-dodecyl.

These alkyl groups include, for example, halogen, hydroxyl group, carboxyl group, nitro group, cyano group, amino group,
It may be substituted with a substituent such as an alkoxy group, an alkoxycarbonyl group, an acyl group, or an acyloxy group.

Examples of the aryl having 6 to 12 carbon atoms for R1 include phenyl, tolyl, naphthyl, and the like. These aryl groups may be substituted with the same substituents as the above substituents exemplified as substituents for alkyl groups.

The optionally substituted alkyl having 1 to 12 carbon atoms and aryl having 6 to 12 carbon atoms of R3 or R4 in the group -NR3R4 represented by R1 can be exemplified by the same groups as mentioned above for R1. In addition, examples of cycloalkyl having 5 to 10 carbon atoms for R3 or R4 include cyclobentyl, cyclohexyl, and compounds of the above formula (I[>-1) such as bis(3,5-dichloro-4-
hydroxyphenyl) sulfone, bis(3,5-dibromo-4-hydroxyphenyl) sulfone, 3,5-dichloro-4-hydroxybenzenesulfonic acid amide, 3,
Examples include 5-dibromo-4-hydroxybenzenesulfonic acid amide and 3,5-dibromo-4-hydroxybenzenesulfonic acid N-methylamide.

In the above formula <II)-2, the optionally substituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, and aryl having 6 to 12 carbon atoms as R2 is represented by the formula (
The same groups as those exemplified above for n)-1 can be exemplified. Also, as the group -NR6R7, the group -NR6R7
The same groups as those exemplified above for 3 and R4 can be exemplified. As R5 of the group -ORs of R2. Also, the group R
The same groups as those exemplified above for 3 and R4 can be exemplified.

Examples of the compound of the above formula (IF)-2 include bis(3
．． 5-dichloro-4-hydroxyphenyl>ketone, bis(3,5-dibromo-4-hydroxyphenyl)ketone, methyl 3.5-dichloro-4-hydroxybenzoate, 3.5-dibromo-4-hydroxybenzoic acid Methyl,
Methyl 3,5-dibromo-4-hydroxybenzoate, 3
, 5-dibromo-4-hydroxybenzoic acid amide, 3,
Examples include 5-dibromo-4-hydroxybenzoic acid N-ethylamide and 3,5-dibromo-4-hydroxybenzoic acid.

Examples of the compound of formula (n)-3 include 3.5-dichloro-4-hydroxybenzonitrile, 35-dibromo-4-hydroxybenzonitrile, and the like.

As the compound of the above formula (II)-4, for example, 3.5-
Examples include dichloro-4-hydroxynitrobenzene and 3,5-dibromo-4-hydroxynitrobenzene.

Among the halogenophenols represented by the above formula (I[), those having a 4-hydroxy-3,5-dichlorophenyl skeleton or a 4-hydroxy-3,5-dibutomophenyl skeleton are preferred, particularly those having the above formula Particularly preferred are compounds represented by (n)-1, especially (3,5-dibromo-4-hydroxyphenyl)sulfone.

Halogenophthalic acids represented by the above formula (DI) and/or halogenophthalic anhydride fvil represented by the above formula (rV) are also suitable catalysts.

In formula <m>, X3 and X4 are the same halogen atoms as defined for X1, such as chlorine or bromine. 1 is the number 0, 1.2 or 3. Of these,
1 is preferably 1, 2 or 3, particularly preferably 2 or 3. In formula <m>, R8 has the same definition as R2 in formula (If) above, and therefore, as R8, the same groups as exemplified for R2 can be exemplified.

Furthermore, in formula (IV), the definitions of X3, Xa and ρ are the same as those in formula (II>) above.

Examples of the compounds represented by formula (III) and formula (IV) include the following compounds.

(i) dicarboxylic acids and their anhydrides; e.g. 3,
4,5.6-tetrabromo (or tetrachloro) phthalic acid. 3,4,5.6-tetrabromo (or tetrachloro) phthalic anhydride. 3,4.5 -}ribromo (or trichloro) phthalic acid. 3.4 .5-Tribrome (or trichloro)phthalic anhydride, 3,4.6-
}Librome (or trichlor>phthalic acid.3.4.6
-Tribrome (or trichlor) phthalic anhydride, etc.

(ii) dicarboxylic acid monoester; for example 3,
4, 5. 6 Tetrabrome (or Tetrachlor) -
Phthalic acid monomethyl ester. 3,4,5.6-Tetrabromo (or tetrachlor) monophthalic acid monoethyl ester. 3,4,5.6-Tetrabromo (or tetrachlor) monophthalic acid monopropyl ester, 3,4,
5.6-tetrabromo (or tetrachlor) monoisopropyl phthalate ester, 3, 4, 5. 6-
Tetrabrome (or tetrachlor〉-phthalic acid monobenzyl ester, 3,4,5.6-tetrabrome (
or tetrachlor〉-phthalic acid monophenyl ester, etc.

En Dicarboxylic acid monoamide; for example 3, 4, 5.
6-tetrabromo (or tetrachlor) monophthalic acid monoamide, N-methyl-3. 4, 5. 6-tetrabromo (or tetrachlor) monophthalic acid monoamide,
N-ethyl-3. 4, 5. 6-tetrabrome (or tetrachlor)-phthalic acid monoamide, N-probyl-3. 4. 5. 6-tetrabrome (or tetrachlor>-phthalic acid monoamide, N-decyl-3, 4
, 5. 6-tetrabromo (or tetrachlor) monophthalic acid monoamide, N-phenyl 3, 4, 5.
6-tetrabromo (or tetrachloro)-phthalic acid monoamide, etc.

■ Ketocarboxylic acids; e.g. 2-carboxy-3,4,
5. 6-tetrabromo (or tetrachlor)-phenyl-remethylketone, 2-tetrabromo-3,4,
5. 6-tetrabrome (or tetrachlor)-phenylethyl ketone, etc.

Among these, the above-mentioned dicarboxylic acids and their anhydrides are preferred, and tetrachlorophthalic acids, tetrabromophthalic acids and their anhydrides are more preferred, among which 3.
4, 5. 6-tetrabrome (or tetrachlor)
Particularly preferred are monophthalic acid, 3,4,5,6-tetrabromo (or tetrachloro)-phthalic anhydride.The amount of these acidic catalysts used is not particularly limited, but depending on the iminoether group of the polycyclic iminoether used, preferably 0.01 to 20 mol%, more preferably 0.05
The amount is about 15 mol %, particularly preferably about 0.1 to 10 mol %.

As the radical catalyst used in the present invention, organic peroxides are preferably used, and specifically, getone peroxide such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl isobutyl ketone peroxide, cumene hydroperoxide, tertiary peroxide, etc. Hydroperoxides such as butyl hydroperoxide, peroxy esters such as tert-butyl peroxyoctoate, tert-butyl peroxybenzoate, 1,3-bis(t-butylperoxyisobutyl)benzene, Dicumyl peroxide, dialkyl peroxide such as tris(tert-butyl peroxy) triazine, diacyl peroxide such as isobutyryl peroxide, lauroyl peroxide, penzoyl peroxide, etc., 1.1-
Peroxy ketals such as tertiarybutylperoxy-3.3.5-}limethylcyclohexane, 1,1-ditertiarybutylperoxycyclohexane, 2,2-di(di-tertiarybutylperoxy)monobutane, etc. Examples include percarbonates such as tert-butyl peroxyisobrovinolecarbonate, bis(4-tert-butylcyclohexyl) peroxy dicarbonate, di-3-methoxybutyl peroxy dicarbonate, and the like.

These radical catalysts can be used alone or in combination of two or more. The amount of these radical catalysts used is determined by the component (
0.05 to 15% by weight based on the total amount of B) and component (C)
, preferably 0.1 to 10% by weight, particularly preferably 0.1 to 10% by weight.
The amount is about 2 to 5% by weight. To the above radical catalyst, organic acid salts of polyvalent metals such as octolates or nanthenates of cobalt, manganese, iron + S + other heavy metals, and if necessary, tertiary amines such as dimethylaniline, dimethyl para-toluidine, etc. are added. Polymerization accelerators, hydroquinone, naphthoquinone, tertiary butyl tethers,
Adding small amounts of polymerization inhibitors such as p-penzoquinone, butylated hydroxytoluene, and nitroxide radicals is also a good option for controlling the reaction rate and improving pot life.
It can be implemented properly.

As a method of subjecting the thermosetting resin composition of the present invention to a thermosetting reaction to obtain a precept, for example, component (A), (B) precept,
A thermosetting composition is prepared by physically intimately mixing component (C), an acidic catalyst, and a radical catalyst, each solid and/or liquid, and melting the mixture by heating if necessary. A method of filling a mold of a desired shape and causing a heating reaction in the mold (one-component method), or component (A),
Divide the components (B) and (C) into arbitrary proportions, mix them separately and intimately, and if necessary, dissolve them to obtain two types of mixtures, and mix these two types of mixtures using a mixing head, etc. Examples include a method (two-component mixing method) in which a thermosetting compound is formed and then directly injected into a mold of a desired shape that has been heated to a reaction temperature in advance to cause a reaction. In the case of the above two-component mixing method, (A) precepts are the main;
(B) component as the subordinate, and this as necessary (C) component dissolved in the precept, and (B) precept as the main, (A> precept as the subordinate, and this as necessary) ( It is also possible to preheat each of the components dissolved in component C) and use the resulting two-part mixture.Also, in the case of a two-part mixing method, the acidic catalyst (
It is preferable to contain the radical catalyst in the component which mainly consists of component (B), and it is preferable to contain the radical catalyst in the component which mainly consists of component (A).

The reaction temperature varies depending on the components (A), (B), and (C) used, the types of acidic catalysts and radical catalysts, and their usage ratios, but is preferably 35 to 280°C, more preferably 45°C. ~240°C, particularly preferably 55-200°C
It is about ℃.

The reaction time may be sufficient as long as it is sufficient to harden the target resin, and this time varies depending on the type of raw materials used, the proportion used, the reaction temperature, etc., but is preferably 1.
The time is about 0 seconds to 90 minutes, more preferably 20 seconds to 60 minutes, particularly preferably about 30 seconds to 45 minutes.

Although the reaction can be carried out at normal pressure to elevated pressure, it is preferably carried out under an inert gas atmosphere such as nitrogen or argon in order to prevent water from entering the atmosphere and oxidative deterioration of the resin.

Furthermore, it may be preferable to improve the physical properties by heat-treating the reaction product at a temperature higher than the reaction temperature, if necessary.

The thermosetting resin composition of the present invention may optionally include thermoplastic polymer fibers, fibrous reinforcing materials such as carbon fibers and glass fibers, various fillers, fillers, pigments, colorants, oxidation stabilizers, ultraviolet rays, etc. An absorbent, a mold release agent, etc. can be contained. For example, in the case of a fibrous reinforcing material, the above-mentioned fibrous reinforcing material is inserted into a reaction mold in advance in the form of a fabric, mat, etc. as necessary, and the thermosetting resin composition of the present invention is applied thereon. be able to.

In such a case, the heating reaction of the present invention is carried out, for example, in the presence of a fibrous reinforcing material, and it goes without saying that a curable resin containing these reinforcing materials, such as a composite, can be obtained. .

According to the present invention, the above objects and advantages of the present invention further include, together with the above components (A), (B) and (C),
(D) Contains at least 2 equivalents of at least one group selected from the group consisting of carboxyl group, hydroxy group, amino group, epoxy group, and carboxylic acid anhydride group in the molecule, but does not have ethylenically unsaturated bonds These components are combined with the above polycyclic imino ether (A+
and the ethylenically unsaturated monomer (C) 0 to 40 per 100 parts by weight of the ethylenically unsaturated compound (B).
0 parts by weight and the above compound (D) in a ratio of less than 1.2 equivalents to the above polycyclic imino ether <A>,
It has become clear that similar effects can be achieved by heating the reaction in the coexistence of an acidic catalyst and a radical catalyst.

(As the component D>, for example, an organic polycarboxylic acid having no ethylenically unsaturated bond or an intramolecular anhydride, an organic polyhydroxy compound, an organic polyamino compound, an organic polyepoxy compound, an organic hydroxycarboxylic acid, an organic aminocarboxylic acid, or Compounds containing at least 2 equivalents of the same or different functional groups in the molecule, such as organic hydroxyamino compounds, are preferably used.

Specifically, examples of organic polycarboxylic acids include phthalic acid, halogenated phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, dibromotetrahydrophthalic acid, succinic acid, adipic acid, Examples include saturated dibasic acids such as glutaric acid, pimelic acid, succinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc. and polybasic acids such as trimellitic acid, hemimelic acid, trimesic acid, benzene tetracarboxylic acid, etc. be done. Particularly preferred organic polycarboxylic acids include adivic acid, glutaric acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, and isophthalic acid.

As the acid anhydride of the organic polycarboxylic acid, among the above-mentioned organic polycarboxylic acids, intramolecular anhydrides of polycarboxylic acids having a 1,2- or 1,3-dicarboxyl group are preferred. can.

Specifically, aliphatic 1,2- or 1,3-dicarboxylic acid anhydrides such as succinic anhydride, glutaric anhydride, methylsuccinic anhydride, cyclohexane-1.2-dicarboxylic acid anhydride, 3- or 4-methyl cyclohexane-1,2
-Alicyclic 1,2-dicarboxylic anhydrides such as dicarboxylic anhydrides, phthalic anhydride, biromellitic anhydride, 3
．． 3', 4. Examples include aromatic 1,2-dicarboxylic anhydrides such as 4'-benzophenonetetracarboxylic anhydride. Among these, aliphatic dicarboxylic anhydrides such as succinic anhydride and glutaric anhydride, cyclohexane-1,2-dicarboxylic anhydride, and phthalic anhydride are particularly preferred.

Specific examples of polyhydroxy compounds include, for example, aliphatic hydroxy compounds such as ethylene glycol, propylene glycol, trimethylene glycol, butanediol, hexanediol, octanediol, decamethylene glycol, diethylene glycol, triethylene glycol, glycerol, and triethylene glycol. Methylolpropane, pentaerythritol, polyoxyethylene glycol, neoventrene glycol, polyoxytetramethylene glycol, bishydroxyethyl terephthalate, bishydroxyethyl isophthalate, etc.; as alicyclic hydroxy compounds, cyclohexanedimethanol,
Aromatic hydroxy compounds such as dihydroxycyclohexane and trihydroxycyclohexane include hydroquinone, resorcinol, methylhydroquinone, chlorohydroquinone, t-butylhydroquinone, t-aluminumhydroquinone, fluorohydroquinone, promhydroquinone, 2,5-dichlorohydroquinone, and pyrogalloquinone.
1 re, catechol. 1,3.5-trihydroxybenzene, 2.2-bis(4-hydroxyphenyl)propane, 4.4'-dihydroxydiphenyl, 4.4'-dihydroxydiphenyl ether. 4.4'-dihydroxydiphenyl sulfide. 4.4'-dihydroxydiphenylmethane, 1.1-bis(4-hydroxyphenyl>cyclohexane, phenolphthalein, 1,1-
Bis(4-hydroxyphenyl)ethane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2
, 2-bis(3.5-dimethyl-4-hydroxyphenyl)propane, 3.4'-dihydroxydiphenyl ether, dihydroxynaphthalene, etc.; as halogenated bisphenols, 2.2-bis(3-chloro-4-hydroxyphenyl) Propane, 2,2-bis(3,5-dichloro-4-phenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 22-bis(3,5-dibromo-4- hydroxyphenyl)propane, bis(3,5-dichloro-4-hydroxyphenyl)methane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)ethane, 1,1-bis(3,5- Dibromo-4-hydroxyphenyl)ethane, bis<3.
5-dichloro-4-hydroxyphenyl〉sulfone, bis(3,5-dibromo-4-hydroxyphenyl〉sulfone, bis(35-dichrome-4-hydroxyphenyl〉also sulfone, 1,1-bis(3,5 -dibromo-4-hydroxyphenyl〉cyclohexane,1,1-bis(3
, 5-dibromo-4-hydroxyphenyl〉cyclohexane, bis(3,5-dichloro-4-hydroxyphenyl) ether, bis(3,5-dibromo-4-hydroxyphenyl〉ether.bis(3,5-dibrom- 4-
Examples include hydroxyphenyl sulfide, bis(3,5-dibrom-4-hydroxyphenyl)ketone, etc., and polyol compounds obtained by conventionally known production methods in which phenols and aldehydes are dehydrated and condensed in the presence of an acid or alkali catalyst. be done.

As for the last polyol compound, phenols include, for example, phenol, cresol, hydroquinone,
Examples include aromatic hydroxyl group-containing compounds such as resorcinol, xylenol, α-naphthol, β-naphthol, and dihydroxynaphthalene. Among these, phenol is preferred. In addition, as aldehydes,
Examples include formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, benzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, and terephthalaldehyde.

Among these, formaldehyde is preferred.

Examples of polyhydroxy compounds include polyhydroxy compounds having an alcoholic hydroxyl group, 2,2-bis(3,5
-dichloro-4-hydroxyphenyl>propane, 2.
Preferred are resols obtained from 2-bis(3,5-dibromo-4-hydroxyphenyl)propane, phenol novolak, and phenol-formalin.

Examples of the organic polyamino compound used in the present invention include aliphatic, alicyclic, and aromatic compounds having two or more primary amino groups and/or secondary amino groups in the molecule. Specifically, examples of aliphatic polyamine compounds include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, and trimethylhexamethylenediamine. Diethylenetriamine, triethylenetetramine, dodecamethylene diamine, neopentylene diamine, etc.; alicyclic polyamine compounds such as diaminocyclohexane, isophorone diamine, piperazine, 1
-(2-aminoethyl)piperazine, bis(4-aminocyclohexyl>methane, bis(aminomethyl>cyclohexane), etc.; Also, as an aromatic polyamine compound, 4
, 4'-diaminodiphenyl methane, 4.4'-diaminodiphenyl sulfone, 3j'-diaminodiphenyl sulfone, 4.4'-diaminodiphenyl ether, 3.
4'-diaminodiphenyl ether, 4.4'-diaminobenzophenone, 3.3'-diaminobenzophenone, p-phenylenediamine, m-phenylenediamine,
P-xylylene diamine, m-xylylene diamine, diamino naphthalene, 4,4'-diaminodiphenyl sulfide, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,2-dianilinoethane, diethyldiaminotoluene, etc. I can give an example. Of these,
Aromatic polyamine compounds are particularly preferred, but compounds (B
) and (D) contain an epoxy group, aliphatic and alicyclic amines are also preferably used.

The organic polyepoxy compound used in the present invention is a polyepoxy compound having two or more epoxy groups in the molecule, and the following compounds are exemplified.

1) Glycidyl ether compounds: 2,2-bis(4-hydroxyphenyl>propane (bisphenol A>), 4.4'-dihydroxydiphenylmethane, 4.4'-dihydroxydiphenylsulfone, resorcinol, phenol novolak, cresol novolak, Aromatic polyols such as resorcinol novolac, naphthol novolac, dihydroxynaphthalene, dihydroxynaphthalene novolac, etc.; aromatic hydroxy compounds such as phenol, dihydroxybenzene, naphthol, dihydroxynaphthalene, etc., and glyoxal, glutaraldehyde, p-hydroxybenzaldehyde, benzaldehyde, etc. Polyols obtained by dehydration reaction with aldehydes such as, for example, under an acidic catalyst; butadiol, polypropylene glycol,
Glycidyl ethers of polyols such as polyhydric alcohols such as polyethylene glycol, glycerol, etc. and precursor polymers thereof.

2) Glycidyl ester compounds: Glycidyl esters of dicarboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, naphthalene dicarboxylic acid, etc., and precursor polymers thereof.

31 N-glycidyl compound: A compound in which the active hydrogen bonded to the nitrogen atom of a nitrogen-containing compound such as aniline, incyanuric acid, methylene dianiline, etc. is replaced with a glycidyl group.

4) Glycidyl ether ester compound'! IJ:p-
Glycidyl ether esters of hydroxycarboxylic acids such as hydroxybenzoic acid and hydroxynaphthonic acid.

5} Others: Epoxy resins obtained from alicyclic compounds such as cyclopentadiene and dicyclopentadiene, triglycidyl compounds of p-aminophenol, vinylcyclohexene dioxide, and the like.

Among these, diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 4.4'- diglycidyl ether of dihydroxydiphenylmethane, polyglycidyl ether of phenol novolak, polyglycidyl ether of naphthol novolac, polyglycidyl polyol obtained by dehydrating phenol with glycioxal, glutaraldehyde, benzaldehyde or p-hydroxybenzaldehyde under acidic catalyst. Ether, diglycidyl ether of polypropylene glycol, diglycidyl ether of polyethylene glycol, diglycidyl ether of butanediol, diglycidyl ether of glycerol, triglycidyl ether of glycerol,
N,N,Nl,Nl-tetraglycidylmethylene dianiline, diglycidyl ether ester of p-hydroxybenzoic acid, diglycidyl ether ester of 2-hydroxy-6-naphthoic acid, triglycidyl compound of p-aminophenol, and Vinyl cyclohexene dioxide is preferred. In particular, diglycidyl ether of bisphenol A, polyglycidyl ether of phenol novolak, polyglycidyl ether of α-naphthol novolak, and polyols obtained by dehydrating phenol with glyoxal, glutaraldehyde, benzaldehyde, or p-hydroxybenzaldehyde under acidic catalysts. Polyglycidyl ether of polypropylene glycol, diglycidyl ether of polyethylene glycol, diglycidyl ether of butanediol. diglycidyl ether of glycerol, triglycidyl ether of glycerol,
Preferred are N,N,N',N'-tetraglycidylmethylene dianiline, triglycidyl compounds of p-aminophenol, and vinylcyclohexene dioxide. These can be used alone or in combination of two or more.

Examples of compounds containing different functional groups include organic hydroxycarboxylic acids such as p-hydroxybenzoic acid and salicylic acid; organic aminocarboxylic acids such as p-aminobenzoic acid and DL-alanine; and aminophenol and ethanolamine. Organic hydroxyamino compounds; and carboxylic acid monoanhydrides such as trimellitic anhydride are exemplified, among which p-hydroxybenzoic acid,
Preferred are organic hydroxycarboxylic acids such as salicylic acid, trimellitic anhydride, and aminophenol.

As the compound (D), one kind or a mixture of two or more kinds of the above-mentioned compounds can be used.

In the present invention, the above polycyclic imino ether (A),
The ethylenically unsaturated compound (B) and the ethylenically unsaturated monomer (C) contain 0 to 400 parts by weight of component (C) per 100 parts by weight of the total of (A) and (B) components. used.

If the above range is exceeded, the viscosity of the resin compound may increase, causing difficulties during molding, the reactivity of the composition may decrease, requiring high temperatures for reaction, or the physical properties of the obtained material or shape may be insufficient. I don't want it to disappear. Further, a preferred usage ratio is 10 to 300 parts by weight of component (C) based on the same criteria as above, and a more preferred usage ratio is 20 parts by weight of component (C) based on the same criteria as above. ~250 parts by weight.

In addition, the above precept (D) is such that the sum of carboxyl groups, hydroxy groups, amino groups, epoxy groups, and carboxylic acid anhydride groups of component (D) is 1 with respect to the equivalent of the cyclic imino ether group.
．． It is less than 2 equivalents, preferably less than 1.0 times the equivalent, more preferably less than 0.9 times the equivalent.

By using such a saturated compound (D), it becomes possible to advantageously control the reaction and adjust the crosslinking density.

Here, when using component (D), as component (B), a high molecular compound can also be used in addition to the above-mentioned low molecular compounds.

Preferred examples of such polymer compounds include unsaturated polyesters having carboxyl groups or hydroxyl groups.

(Bl) Some unsaturated polyesters use α,β monounsaturated dibasic acids and/or their ester-forming derivatives as the dibasic acid component, or combine these with saturated dibasic acids and/or their ester-forming derivatives. It is produced by a known method using a polyhydric alcohol and/or an organic epoxide such as propylene oxide as the alcohol component.Molecular weight: 500 to t
An oooo unsaturated polyester is preferred.

Examples of α,β monounsaturated dibasic acids include maleic acid,
Halogenated maleic acid, fumaric acid, citraconic acid, itaconic acid, halogenated itaconic acid, 5-norbornene-2
．． 3-dicarboxylic acid, methyl-5-norvonolene-2
．． Examples include 3-dicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, tetralactophthalic acid, and intramolecular acid anhydrides or alkyl esters thereof. In addition, examples of saturated dibasic acids include phthalic acid, halogenated phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid,
Hexahydrophthalic acid, hexahydrophthalic anhydride, methylhexahydrophthalic acid, methylhexahydrophthalic anhydride, dibromotetrahydrophthalic acid, dibromotetrahydrophthalic anhydride, succinic acid, succinic anhydride, adivic acid, glutaric acid, pimelic acid , succinic acid, azelaic acid, sebacic acid, or their alkyl esters. In addition, monobasic acids such as acrylic acid, methacrylic acid, propionic acid, butyric acid, valeric acid, higher fatty acids, benzoic acid, p-hydroxybenzoic acid, octylic acid, trimellitic acid, hemimellitic acid,
Polybasic acids such as trimesic acid, benzene tetracarboxylic acid, etc. can be used as modifiers.

Examples of polyhydric alcohols include ethylene glycol,
Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dialobylene glycol, tripropylene glycol, polypropylene glycol, 1,3- or 1,4-butylene glycol, tetramethylene glycol, 1,6-hexanediol, neobentyl Examples include glycol, hydrogenated bisphenol A, and ethylene oxide and/or propylene oxide adducts of bisphenol A.

The polyhydric alcohol is used in a substantially equivalent amount to the dibasic acid component, or in an excess amount of 20 mol% or less. Also,
Amyl alcohol, hexyl alcohol, if necessary
Monohydric alcohols such as pentyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, tetrahydrofurfuryl alcohol, glycerin, pentaerythritol, trimethylolethane, trimethylolpropane, trimethylolbutane. Polyhydric alcohols such as sorbitol, erythritol, mesoerythritol, etc. can be used as denaturing agents.

Further, examples of the organic epoxide include ethylene oxide, 1,2-propylene oxide. Alkylene oxides such as shrimp chlorohydrin; glycidyl ethers such as methyl glycidyl ether, ethyl glycidyl ether, allyl glycidyl ether; and glycidyl esters such as methyl glycidyl ester, ethyl glycidyl ester, allyl glycidyl ester, and the like. These polyhydric epoxides are also used in a substantially equivalent amount to an excess of 20 mol % or less relative to the dibasic acid component.

Unsaturated polyesters may be used in combination of two or more types,
It may also be used in combination with a low molecular weight compound.

The unsaturated polyester is advantageously used in a weight ratio of polycyclic iminoether:unsaturated polyester of 1:15 to 15:1, more preferably 1:12 to 12:1.

As the method of subjecting the thermosetting composition containing the Dl component (of the present invention) to a thermosetting reaction to form a prescriptive product, a method similar to the method described above can be adopted. When a two-component method is adopted For this purpose, it is preferable to form a two-part precept, with the (D) precept as the main or secondary component, together with the (B) component.

(D) Regarding the thermosetting composition containing the precepts, it should be understood that the above descriptions apply as is to any points not described here.

Any of the above-mentioned thermosetting compositions of the present invention contain a small amount of other components that are different from the <D) component and can undergo an addition reaction with the component (A), the component (B), and the component (C). can do. Examples of the components include isocyanates, saturated monocarboxylic acids, saturated monohydroxy compounds, saturated monoamines,
Saturated monoepoxy and the like can be mentioned.

When comparing the thermosetting resin composition of the present invention using the same radical initiator, the reaction time can be shorter than that of an unsaturated polyester resin, and therefore cycle-up is possible. In addition, the obtained thermosetting resin molded product has excellent physical properties such as mechanical properties, chemical resistance, and heat resistance, and has extremely excellent properties such as no cracking even in systems without the addition of reinforcing materials.

(e) Examples Hereinafter, the present invention will be explained in detail with reference to Examples, but the Examples are for illustration purposes only and the present invention is not limited thereto.

In the examples, "part r" means "part by weight", and the heat distortion temperature is DMA (
The temperature was measured using a dynamic thermomechanical property measuring device at a heating rate of 10° C./min.

Examples 1 to 10 and Comparative Example 1 Unsaturated polyester made from 200 mol% maleic anhydride, 100 mol% isophthalic acid, and 300 mol% propylene glycol (viscosity/Stokes: 5.6, acid value/
mgKOH/g: 3g. Unsaturated bond content/mol/g measured by dodecyl mer-butane method: 0.2
95) 1.00 parts of styrene, 1.00 parts of styrene, and 2.0 parts of the specified amount shown in Table 1. 2'-m-phenylenebis(2
-oxazoline), compound (C), and catalyst were placed in a glass reactor, mixed well, and then replaced with nitrogen and immersed in an oil bath at 90°C. The reaction mixture was once uniformly dissolved and then cured for the time shown in Table 1, resulting in light brown to pale yellow resins.

For comparison, 2. A similar experiment was conducted on the system except for excluding 2'-1m-phenylenebis(2-oxazoline), compound (C), and a portion of the catalyst.

Table 1 shows the heat distortion temperatures of the obtained resins, and it can be seen that all of them have excellent heat resistance. Furthermore, all the resins were strong and exhibited excellent solvent resistance with little dissolution or swelling even when immersed in acetone.

Examples 11 and 12 Unsaturated polyester (“Yubica 3464” manufactured by Nippon Upica)
;Styrene diluted> or maleic anhydride 100
mol%, unsaturated polyester made from 100 mol% of propylene glycol (viscosity/Stokes: 3.6. acid value/mgKo}I/g: 39, unsaturated bond content/not/g: 0.417) 2.00 parts of rUPE-B J diluted with the same weight of styrene. 2.41 parts of 2'-1m-phenylenebis(2-oxazoline),
4. 1.58 parts of 4'-methylene dianiline, 0.02 parts of Kayaestele O-50 manufactured by Kayaku Nouri ■, 140.02 parts of Parriki Dox, and 0.20 parts of ethyl p-toluenesulfonate were subjected to a glass reaction. The mixture was placed in a vessel, mixed well, purged with nitrogen, and immersed in an oil bath at 100°C. The reaction mixture was once uniformly dissolved and then cured for the time shown in Table 2, resulting in light brown to pale yellow resins.

Table 2 Example 13 Same unsaturated polyester 1 used in Examples 1-10
．． 00 parts of styrene, 1.00 parts of styrene, 2.2'-p-phenylenebis(2-oxazoline>0.20 parts, and 0.10 parts of maleic anhydride were placed in a glass reactor and mixed uniformly in a 100°C oil bath. To this, 0.03 parts of Trigonox 29-B-75 manufactured by Kayaku Nouri ■ and 0.02 parts of ethyl trifluoromethanesulfonate were added, and immediately 1
When it was immersed in a 20°C oil bath, it was cured after 80 seconds to obtain a pale yellow resin. The heat distortion temperature of the resin was 125°C. In addition, all the resins were strong and showed excellent solvent resistance with almost no dissolution or swelling even when immersed in acetone.

Example 14 Same unsaturated polyester 6 used in Examples 1-10
component A consisting of 0 parts, 70 parts of styrene, 63 parts of 4.4'-methylene dianiline, and 4 parts of diethyl sulfate, and 70 parts of the above unsaturated polyester. 60 parts of styrene, 2.2
67 parts of '-m-phenylenebis(2-oxazoline) and 2 parts of Kayaester 0-50 manufactured by Kayaku Nouri ■,
Component B consisting of 2 parts of Parriki Dox 14 was melted at 80° C. in a nitrogen stream to obtain liquids A and B.

The above solutions A and B were injected into a mixing head heated to 90°C and mixed, and immediately filled into a mold heated to 100°C and allowed to react for 5 minutes. The resulting molded product was transparent, bubble-free, and strong, and had a heat distortion temperature of 164°C.

Example 15 Same unsaturated polyester 5 used in Examples 1-10
00 parts, 500 parts of styrene, 90 parts of 4,4'-methylene dianiline, 2. 2'-m-phenylenebis(2
210 parts of 1-oxazoline) were uniformly dissolved at 80°C and charged into a tank kept at 60°C. There, 20 parts of Kaya Ester O-50 manufactured by Kayaku Nouri ■ and 10.5 parts of diethyl sulfate were added, followed by stirring. Degassed under reduced pressure and then replaced with nitrogen. Add this solution to 100 kg/cd in advance.
The mold was heated to 0.degree. C., and a glass fiber cloth was put therein so as to have a Vf of 26%.The mold was injected under pressure, held at 100.degree. C. for 30 minutes, and then taken out.

The obtained molded plate had no bubble cracks, and its physical properties are shown in Table 3, and it had excellent mechanical properties and particularly good durability.

Table 3 Ne4 TOYO BALDWIN Tensilon CR-
7000/UTM*5 ■Toyo Seiki Seisakusho HDT &
V. S. P. 7. 7 Star Examples 16 and 17 Same unsaturated polyester 1 used in Examples 1-10
00 parts, 100 parts of styrene, and the amounts shown in Table 4.
．． 4'-methylene dianiline, 2. 2'-m-
After homogeneously dissolving phenylene bis(2-oxazoline) at 85°C, ethyl p-toluenesulfonate and Kayaester 0-5 manufactured by Kayaku Nouri ■ were added to it in the amounts shown in Table 4.
0 and 2 parts of Parriki Dox 14 were added thereto, and the mixture was placed in a mold preheated to 90° C. and reacted for 10 minutes. The obtained board was transparent and free of bubbles. This molded plate was heat-treated at 150°C for 5 hours, and the mechanical properties and heat resistance were evaluated for Tensilon CR-7000/υTM manufactured by TOYO BALDWIN and HDT manufactured by Toyo Seiki Seisakusho.
&V. S. P. Table 4 shows the results of measurements using a T tester, and the results showed that it was extremely tough and had high heat resistance.

Examples 18-19 Same unsaturated polyester 3 as used in Examples 1-10
0 parts, 30 parts of styrene and 2.0 parts of styrene in the amounts shown in Table 5. 2
' After dissolving 1m-phenylenebis(2-oxazoline) and the compound (DJ) uniformly at 100°C, add 1.1 part of diethyl sulfate to it and Parriki Dox 14 manufactured by Kayaku Nouri ■.
0.6 parts, Perbutyl ZO. 6 parts were added, and this was injected into a mold preheated to 140°C and reacted for 10 minutes. The resulting molded plate was transparent and free of bubbles. Table 5 shows the results of notched Izod impact strength and heat distortion temperature (HDT & V.S.P.T tester manufactured by Toyo Seiki Seisakusho) of the molded plate heat-treated at 150°C for 5 hours. It was strong and strong.

Example 20 Same unsaturated polyester used in Examples 1-10
．． 5 parts, 1.2 parts of styrene, 2. 0.1 part of 2'-, m-phenylenebis(2-oxazoline), 0.07 part of 4,4'-methylene dianiline, 0.0 parts of diethyl sulfate. 00
5 parts, Kayaester O-500 manufactured by Kayaku Nouri ■. 0
48 parts and 0.024 parts of Parriki Dox 14 were charged into a glass reactor, mixed well, and then replaced with nitrogen.
immersed in an oil bath at °C. The reaction mixture was once uniformly dissolved and then hardened in 55 seconds to become a light olive colored resin.

The resulting resin was tough and had a heat distortion temperature of 125°C.

Example 21 Same unsaturated polyester 2 as used in Examples 1-10
0 parts of styrene, 6.8 parts of Epicoat 828, and 0.4 parts of ethyl p-}luenesulfonate; and 10 parts of styrene.2. 2'-m-
8 parts of phenylene bis(2-oxazoline), 1.20 parts of hexamethylene diamine, 0.8 parts of Kaya Ester 0-50 manufactured by Kayaku Nouri ■, and Parriki Dox 140
．． Component B consisting of 4 parts is heated and melted to form liquid A and liquid B.
It was made into a liquid.

The above liquids A and B were injected into a mixing head heated to 90°C and mixed, and immediately filled into a mold heated to 120°C and reacted for 15 minutes. The obtained precipitate was pale yellow, free of bubbles, and strong, and had a heat distortion temperature of 115°C.

Example 22 Same unsaturated polyester 1 as used in Examples 1-10
60 parts, 1.0 part of styrene, 2. 0.2 part of 2'-m-phenylenebis(5,6-dihydro-48-1,3-oxazine), 0.1 part of 4.4'-methylene dianiline
0 parts, Kaya Ester 0-500 manufactured by Kayaku Nouri ■.

02 parts, Bariki Dox 14 0.01 part, dimethyl sulfate 0. 006 parts were charged into a glass reactor, mixed thoroughly, the atmosphere was replaced with nitrogen, and the reactor was immersed in an oil bath at 100°C. The reaction mixture was once uniformly dissolved and then cured in 55 seconds to become a pale yellow resin.

The heat distortion temperature of the obtained resin was 128°C.

Examples 23-32 0.34 part of fumaric acid, 0.5 part of propylene glycol,
2. 2.61 parts of 2'-m-phinylenebis(2-oxazoline), 1.0 parts of styrene, a predetermined amount of compound (D) shown in Table 6, and a catalyst were charged into a glass reactor and mixed well. The tube was purged with nitrogen and immersed in an oil bath at 140°C. The reaction mixtures were once uniformly dissolved and then cured for the time shown in Table 6, resulting in colorless to brown resins.

Table 6 shows the heat distortion temperatures of the obtained resins, and it can be seen that all of them have excellent heat resistance. Furthermore, all the resins were strong and exhibited excellent solvent resistance with little dissolution or swelling even when immersed in acetone.

Examples 33 and 34 Maleic anhydride 0.29 parts, propylene glycol 0,
5 parts, 2.61 parts of 2'-m-phenylenebis(2-oxazoline), 1.0 part of styrene, a predetermined amount of compound (D) shown in Table 7, and a catalyst were charged into a glass reactor and mixed well. After that, the tube was replaced with nitrogen and immersed in an oil bath at 120.degree. The reaction mixtures were once uniformly dissolved and then cured for the time shown in Table 7, resulting in pale yellow resins.

Table 7 shows the heat distortion temperature of the obtained resin, and it can be seen that it has excellent heat resistance. Furthermore, all the resins were strong and exhibited excellent solvent resistance with little dissolution or swelling even when immersed in acetone.

Example 35 Consisting of 4.5 parts of fumaric acid, 3.0 parts of propylene glycol, 3.0 parts of styrene, 10 parts of 2.2'-m-phinylenebis(2-oxazoline), and 10.3 parts of diethyl sulfur. Component A' and 2, θ parts of propylene glycol, 7.0 parts of styrene. 2. 16 parts of 2'-m-phinylenebis(2-oxazoline), 4. 4'-methylene dianiline, 1.
8 parts, Kayaester O-500.26 manufactured by Kayaku Nouri ■
Component B' consisting of 1.5 parts and 0.13 parts of Trigonox 29B-75 was heated and melted to obtain a liquid A and a liquid B, respectively.

The above liquids A and B were injected into a mixing head heated to 130°C and mixed, and immediately filled into a mold heated to 140°C and reacted for 5 minutes. The resulting molded product was transparent, bubble-free and strong, and had a heat distortion temperature of 148°C.

Example 36 0.38 part of itaconic acid, 0.5 part of propylene glycol, 2. 2'-m-phenylenebis(2-oxazoline) 2.61 parts, styrene 1. OO part, 4,4'-methylene dianiline 0.25 part, diethyl sulfate 0.09 part, Kayaku Nouri ■ Kayaester O-50 0.03
After charging 0.02 parts of Parriki Dox 14 into a glass reactor and mixing well, the atmosphere was replaced with nitrogen and immersed in a 120°C oil bath.Then, the oil bath was heated to 140°C at a rate of 4°C/min. Humidity increased. The reaction mixture was once uniformly dissolved, and after the temperature of the oil bath reached 140° C., it hardened in 2 minutes and 30 seconds to become a pale dull orange resin.

The resulting resin was tough and had a heat distortion temperature of 170°C.

Example 37-3 Maleic anhydride 0.98 part, P-}methyl luenesulfonate 0.05 part, Kayaku Nouri ■ Kayaester 0-5
0.04 parts, and 2.0 parts as shown in Table 8. 2' A predetermined amount of 1m-phenylene bis(2-oxazoline), propylene glycol, and styrene was charged into a glass reactor, mixed well, and then purged with nitrogen and immersed in an oil bath heated to 100°C for 5 minutes. It was immersed in an oil bath at 140°C.The reaction mixture was once dissolved uniformly, and after being immersed in an oil bath at 140°C, it was cured for the time shown in Table 8.
It became a pale yellow resin.

Table 8 shows the heat distortion temperature of the obtained resin.

Examples 40 to 45 Unsaturated polyester made from 200 mol% maleic anhydride, 100 mol% isophthalic acid, and 300 mol% propylene glycol (viscosity/Stokes = 5.6, acid value/
mg KOH/g: 38, unsaturated bond content measured by dodecyl mer-butane method/not/g: 0.2
95) 1.00 parts and the prescribed amount of 2.2 as shown in Table 9
'-m-phinylenebis(2-oxazoline), Compound (D), 0.035 parts of diethyl sulfate, and 0.027 parts of Bariki Dox 14 manufactured by Kayaku Nurie ■ were charged into a glass reactor and mixed well. , replaced with nitrogen, 140℃
immersed in an oil bath. The reaction mixture was once uniformly dissolved, and then cured for the time shown in Table 9, resulting in a dark brown to pale yellow resin.

Table 9 shows the heat distortion temperatures of the obtained resins, and it can be seen that all of them have excellent heat resistance. In addition, all the resins were strong and had excellent solvent resistance with almost no dissolution or swelling even when immersed in acetone.

Example 46 Maleic anhydride 100 mol%, propylene glycol 1
Unsaturated polyester synthesized from 00 mol% (viscosity/Stokes = 3.6, acid value/mg KOH/g: 39
, unsaturated bond content/mol/g: 0.417)
1.44 copies, 2. 2'-m-phenylenebis(
1.08 parts of 2-oxazoline, 0.36 parts of cyclohexanedimethanol, 0.05 parts of dimethyl sulfate, and 0.04 parts of Parryoku Dox 14 manufactured by Kayaku Nurie ■ were charged into a glass reactor, mixed well, and then replaced with nitrogen. and immersed in an oil bath at 140°C. The reaction mixture was once uniformly dissolved and then cured, and then cured in 2.2 minutes to become an orange resin.

The heat deformation temperature of the obtained resin was 112° C., and the obtained resin was strong and showed excellent solvent resistance with almost no dissolution or swelling even when immersed in acetone.

Examples 47 and 48 30 parts of the unsaturated polyester used in Examples 40 to 45, 2. 2' 1m-phinilenebis(2
-oxazoline>, cyclohexanedimethanol, 1.04 parts of diethyl sulfate, and 0.83 parts of Parryoku Dox 14 manufactured by Kayaku Nouri Aji were uniformly dissolved in an oil bath at 120°C, and after purging with nitrogen, the mixture was heated to 140°C in advance. It was poured into a heated mold and allowed to react for 15 minutes. The obtained molded plate was pale yellow and transparent with no bubbles. 150 pieces of this molded plate
Notched Izod impact strength and heat distortion temperature of products heat-treated at ℃ for 5 hours (Toyo Seiki Seisakusho HDT & V.
S. P. Table 10 shows the results of the measurements.

Procedural amendment 1. Case Indication Patent Application No. 1 85715 2. Name of the invention Method for producing thermosetting resin, composition and resin (Attachment) Claims (1) (A) The following formula (I) (3001 Polycyclic imino ether represented by Teijin Hachigosha, (B) a low molecular weight ethylenically unsaturated compound having an ethylenically unsaturated bond and a functional group capable of reacting with the cyclic imino ether group of the polycyclic imino ether; and (C) a low molecular weight ethylenically unsaturated compound having an ethylenically unsaturated bond, but The ethylenically unsaturated monomer that does not have a functional group that can react with the cyclic imino ether group of the cyclic imino ether is added to the above per 100 parts by weight of the polycyclic imino ether (A) and the ethylenically unsaturated compound (B). A method for producing a thermosetting resin, comprising using 10 to 400 parts by weight of an ethylenically unsaturated monomer (C) and carrying out a heating reaction in the coexistence of an acidic catalyst and a radical catalyst.

+21 (A) A polycyclic imino ether represented by the following formula (I) 0-C-Re 1 Rf , (B) a functional group that can react with the cyclic imino ether group of the above polycyclic imino ether and an ethylenically unsaturated bond. (C) an ethylenically unsaturated monomer having an ethylenically unsaturated bond but not having a functional group capable of reacting with the cyclic imino ether group of the polycyclic imino ether; , and +D) contains at least 2 equivalents of at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, an epoxy group, and a carboxylic acid anhydride group, but does not contain an ethylenically unsaturated bond. 400 parts by weight of the ethylenically unsaturated monomer (C) O and the above compound (DJ) per 100 parts by weight of the polycyclic imino ether (A) and ethylenically unsaturated compound (B). The above polycyclic imino ether (A)
1. A method for producing a thermosetting resin, characterized in that the thermosetting resin is used in an amount of less than 1.2 equivalents, and the thermosetting resin is heated and reacted in the coexistence of an acidic catalyst and a radical catalyst.

{3} The above polycyclic imino ether (A), ethylenically unsaturated compound (B) and ethylenically unsaturated monomer (
A thermosetting composition containing C) in a proportion of 10 to 400 parts by weight of the ethylenically unsaturated monomer (C) per 100 parts by weight of the total of the polycyclic imino ether (A) and the ethylenically unsaturated compound (B). .

(4) The above polycyclic imino ether (A), ethylenically unsaturated compound (B), ethylenically unsaturated monomer (C)
and a compound (D) having no ethylenically unsaturated bond, per 100 parts by weight of the total of the polycyclic imino ether (A) and the ethylenically unsaturated compound (B), as the ethylenically unsaturated monomer (C) O~ 400 parts by weight and the above-mentioned compound (D) in a ratio of less than 1.2 equivalents based on the above-mentioned polycyclic imino ether (A).

(5) A thermosetting resin obtained by the method of claim 1.

(6) A thermosetting resin obtained by the method of claim 2.

Claims (6)

[Claims] (1) (A) The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) [Here, n is an integer from 2 to 4, and R is an n-valent hydrocarbon residue. and the hydrocarbon residue may be interrupted or substituted with an atom other than carbon or a group containing an atom other than carbon. Z is a direct bond or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and Ra, Rb, Rc, Rd, Re and Rf are the same or different and are a hydrogen atom, methyl, ethyl, propyl, phenyl, tolyl or benzyl . However, when n is 2, R can also represent a direct bond. ] A polycyclic imino ether represented by (B) a low-molecular-weight ethylenically unsaturated compound having an ethylenically unsaturated bond and a functional group that can react with the cyclic imino ether group of the polycyclic imino ether, and (C) an ethylenically unsaturated compound. An ethylenically unsaturated monomer having an unsaturated bond but not having a functional group that can react with the cyclic imino ether group of the polycyclic imino ether is combined with the polycyclic imino ether (A) and the ethylenically unsaturated compound ( Production of a thermosetting resin characterized by using 10 to 400 parts by weight of the ethylenically unsaturated monomer (C) per 100 parts by weight in total of B) and carrying out a heating reaction in the coexistence of an acidic catalyst and a radical catalyst. Law. (2) (A) The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) [Here, n is an integer from 2 to 4, and R is an n-valent hydrocarbon residue. and the hydrocarbon residue may be interrupted or substituted with an atom other than carbon or a group containing an atom other than carbon. Z is a direct bond or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and Ra, Rb, Rc, Rd, Re and Rf are the same or different and are a hydrogen atom, methyl, ethyl, propyl, phenyl, tolyl or benzyl . However, when n is 2, R can also represent a direct bond. ] A polycyclic imino ether represented by (B) a low-molecular and high-molecular ethylenically unsaturated compound having an ethylenically unsaturated bond and a functional group that can react with the cyclic imino ether group of the polycyclic imino ether; (C) An ethylenically unsaturated monomer having an ethylenically unsaturated bond but not having a functional group that can react with the cyclic imino ether group of the polycyclic imino ether, and (D) a carboxyl group, a hydroxy group, an amino group, an epoxy group. and a compound containing at least 2 equivalents of at least one group selected from the group consisting of carboxylic acid anhydride groups in the molecule, but having no ethylenically unsaturated bond, as the polycyclic imino ether (A). 100 to 400 parts by weight of the ethylenically unsaturated monomer (C) and the compound (D) are added to the polycyclic imino ether (A
) in a proportion of less than 1.2 equivalents, and carrying out a heating reaction in the coexistence of an acidic catalyst and a radical catalyst. (3) The above polycyclic imino ether (A), ethylenically unsaturated compound (B) and ethylenically unsaturated monomer (
A thermosetting composition containing C) in a proportion of 10 to 400 parts by weight of the ethylenically unsaturated monomer (C) per 100 parts by weight of the total of the polycyclic imino ether (A) and the ethylenically unsaturated compound (B). . (4) The above polycyclic imino ether (A), ethylenically unsaturated compound (B), ethylenically unsaturated monomer (C)
and a compound (D) having no ethylenically unsaturated bond, per 100 parts by weight of the polycyclic imino ether (A) and the ethylenically unsaturated compound (B) as the ethylenically unsaturated monomer (C). 400 parts by weight and the above-mentioned compound (D) in a ratio of less than 1.2 equivalents based on the above-mentioned polycyclic imino ether (A). (5) A thermosetting resin obtained by the method of claim 1. (6) A thermosetting resin obtained by the method of claim 2.