JPS6026023A - Curable resin composition - Google Patents

Abstract

PURPOSE:A resin composition excellent in the heat resistance of a cured product, obtained by adding a specified aromatic imide and/or amidoimidoimine as a curing agent to an aromatic amine epoxy resin containing a beta-alkylgylcidyl group. CONSTITUTION:A diamine of formula IV (wherein m and n are each 0 or an integer and m+n>0) is produced by reacting aromatic acid anhydrides of formula I (wherein Ar' is a tetravalent aromatic organic group) and/or formula II(wherein Ar'' is a trivalent aromatic organic group) with an organic diamine of formula III (whrerin Ar is a bivalent aromatic organic group) in a molar excess amount over the acid anhydrides in a plar solvent. The above diamine as a curing agent is added to a beta-alkylglycidylamino group-containing aromatic amine- epoxy resin produced from an aromatic amine and a beta-alkylepichlorohydrin to obtain the purpose curable resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable composition having excellent heat resistance and comprising an aromatic imide and/or an amide imide amine and an epoxy resin having a β-alkylglycidyl group.

Conventionally, in order to improve the heat resistance and rigidity of cured epoxy resin products, attempts have been made to introduce imide rings into the intramolecular skeleton. There are many examples in which a general-purpose epoxy resin (for example, diglycidyl ether of bisphenol A) and a curing agent having an imide skeleton are reacted.

We have conducted intensive research with the aim of improving the heat resistance of these general-purpose cured epoxy resins.

Furthermore, the present invention has been achieved in that a cured product having excellent heat resistance, particularly heat decomposition resistance, can be obtained.

It is thought that the presence of the alkyl group suppresses the decomposition of the hydroxyl group generated by curing, and that the heat resistance is improved because the skeleton has an imide ring.

An object of the present invention is to provide an epoxy resin curable composition that has extremely good heat resistance.

That is, the gist of the present invention is as follows.

General formula (I) (wherein Ar is a co-valent aromatic organic group, Ar' is a di-valent aromatic organic group, each of the carbonyl groups is directly bonded to a different carbon atom, and each The pair of carbonyl groups is A
Ar'' is bonded to the adjacent carbon atom in the r' group.
ij is a J-valent aromatic organic group, each of the three carbonyl groups is directly bonded to another carbon atom, and a pair of carbonyl groups are bonded to adjacent carbon atoms in the Ar" group, and n, m is O or a positive integer and is 1m+n
>O. ) and an aromatic diamine containing a β-alkylglycidyl group,
Aromatic acid anhydride represented by the general formula (wherein Ar', Ar" have the above definitions) in a polar solvent such as N,N'-dimethylformamide, N-metal-pyrolidone 1m-cresol, etc. and the general formula (IV) H, N-Ar-NH, in an excess of the number of moles than the number of moles of the acid anhydride,
l1slllllle (IV) (wherein Ar has the above definition) -3= rubonic acid dianhydride, pyromellitic dianhydride 1.2,3
．． b, f-Naphthalenetetracarboxylic dianhydride '7! j
o, 3. a', lI, C-diphenyltetracarboxylic dianhydride, 2. Corbis(3,ti-dicarboxyphenyl)propane dianhydride, bis(3,ti-dicarboxyphenyl)ether dianhydride, 2,6-dichloronaphthalene-/,'I,! ;, g-tetracarboxylic dianhydride, Fujianhydride-/, g, 9. / 0-Tetracarboxylic dianhydride, /, /-bis(,2,,?-dicarboxyphenyl)ethane dianhydride, bis(u,3-dicarboxyphenyl)methane dianhydride, bis(j,+1-
dicarboxyphenyl) sulfone dianhydride, /, /,
/,3,3.3-hexafluoroco,corbis(3,t
i-dicarboxyphenyl)propane dianhydride, trimellitic anhydride, and the like.

4- As the diamines represented by the general formula (■), da, li'-diaminodiphenylpropane, lI, lI'-diaminodiphenylmethane, 3.3'-diaminodiphenylmethane, da, lI'-diaminodiphenyl sulfide, 3. .3'-diaminodiphenylsulfone, +, 4
t'-diaminodiphenylsulfone, lI, lI'-diaminodiphenyl ether, 3.3'-dimethyl-+
, lI'-diaminodiphenylmethane, 3-methyluda, 44'-diaminodiphenylmethane, 3,3'-dietheruta, ri'-diaminodiphenylmethane, 3-aminodiphenyl sulfone, 3,3'-diethyl-a, +'-
Cyanodiphenylpropane, 3,3'-dimethyl-p
, lI'-diaminobenzophenone, 3.3'-diaminodiphenylmethane, ? ,,? '-diaminodiphenyl ether, 2.4<-7mi/)ruene.

Tip 6-diamittoluene, co, diaminoanisole, 2,4'-diaminomonochlorobenzene, co,
Terdiaminofluorobenzene, m-phenylenediamine, p-phenylenediamine, 7. ．． 7'-diaminobenzophenone, l,3-bis(3-aminophenol)benzene, 9,9-bis(ter-aminophenyl)
Examples include fluorene. A mixture of these diane types can also be used.

The reaction is obtained by adding the diamine spreading promoter in the presence of the diamine spreading promoter and carrying out a heating reaction under known polymerization conditions for producing an imide polymer or an amide-imide polymer.

− M − When reacting in a two-step method, add a ring-closing agent after the addition reaction is completed,
Obtained by ring closure.

After the reaction is completed, the solvent and excess β-alkyl epichlorohydrin are removed by distillation or the like to obtain the desired β-alkylglycidylamino group-containing aromatic amine epoxy resin. Examples of the β-substituted alkyl group include methyl, ethyl, propyl, butylene, and the like, with a methyl group being particularly preferred. That is, β-methylglycidylamino group-containing aromatic amine epoxy resin is preferred.

Examples of the solvent used here include 1.

N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-pyrrolidone, N-methyl lactam, N,N-dimethylacetamide, hexamethylene phosphorylate, tetramethylene sulfone, butyrolactone, methanol, ethanol, methyl cellosolve Examples include alsan and the like.

Examples of reaction accelerators include sodium hydroxide, potassium hydroxide, lithium hydroxide, hydroxide specific gravity such as sodium carbonate, calcium carbonate, boron trifluoride, boron trifluoride-ethyl ether complex, and aluminum chloride. , 7th class ammonium salts such as methylnitrous ammonium chloride, tetramethylammonium bromide, tetraethelammonium bromite, tetraethelammonium idodide, lithium compounds such as lithium chloride, lithium acetate, etc.1. ;I can get lost.

Examples of ring agents include alkaline earth hydroxides such as sodium hydroxide and magnesium hydroxide, organic acid alkali salts such as formic acid, thorium, and sodium acetate, and trimethylene may be used as a ring-closing catalyst. .

Used in the present invention. The aromatic amines to be reacted with β-alkylepichlorohydrin include aromatic amines other than aromatic imides or amide imide polymers, such as aniline, 〇-, p-)luidine, m-, p-aminophenol, m- , p-phenylenediamine, J, 4
'-Diaminotoluene, 2,6-diaminotoluene, diaminotoluene, ? , J'-diaminodiphenylmethane.

da, da'-diaminodiphenylmethane, 3. 3'-diaminodiphenylsulfone, +, +'-diaminodiphenylsulfone, 3. ．． 3'-diaminobenzophenone, +, p'-diaminobenzophenone, 3.3'
-diaminodiphenyl ether, +, lI'-diaminodiphenyl ether, 3.3'-diaminodiphenyl sulfide, p,<z'-diaminodiphenyl sulfide, diaminofluorobenzene, etc. per mole of amino group of Kerara group amines, One mole or more of β-alkylepichlorohydrin is reacted, preferably at a ratio of two moles or more.

The amount of solvent to be used is θ to 0 times the weight of the aromatic amine, but preferably it is θ to /θ times the weight.

If necessary, the reaction accelerator used is preferably from 0005 to 10% by weight, based on the aromatic amines, preferably 1iO0! r~co, 0% by weight is used.

Although the reaction temperature can be raised to the boiling point of the solvent or β-alkylepichlorohydrin, it is generally desirable to carry out the reaction between room temperature and 10°C or less in order to suppress side reactions.

In the ring-closing reaction that is carried out if necessary, the ring-closing catalyst used generally has a ratio of 7 to 1 mole of aromatic amine.
~g moles are used. Open ring mtL.

The aromatic amine-containing epoxy resin can be used as it is, but if it is obtained in the form of a solution, it can be isolated by evaporating the solvent or using a precipitation solvent.

The present invention is achieved by blending the β-alkyl 11-glycidylamino group-containing aromatic amine epoxy resin thus obtained with an aromatic diamine represented by the general formula (D), a curing accelerator and/or Common curing agents may also be used in combination.

Examples of curing accelerators include imidazoles.

Examples include boron trifluoride amine complex and tertiary amines.

Examples of common curing agents include dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, benzophenone tetracarboxylic dianhydride, and the like.

These β-alkylglycidylamino groups contain /, 2-
O0 ratio, good ratio, /, 0-0. The hydroxyl group produced by converting the thus obtained curable resin composition to the alkyl group-substituted carbon atom is bonded to the alkyl group-substituted carbon atom, and has excellent heat resistance, particularly heat decomposition resistance, and is extremely useful.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto in any way.

[Imide polymer: Engineering 0-A] Purification + 2.4'-diaminotoluene 0.411 mat
e and dry N-methyl-copyrrolidone solution in lyslux. /
! ! ；Mote dried N-methyl-virolidone solution to a total amine amount of 3.70 x / 0'' (eq.
-mot/V), 2.4f-diaminotoluene 0.
3? ! mode and N was maintained for one hour to obtain an imide polymer containing an amine end group.

Total amine amount, 2.0/X/0-” (sq-m
o7/f ) -Tmλ 600 [imide polymer=IO-〇] 3.3'-diaminobenzophenone 0.00911 mo
The entire BTDA O,00b 3 mole N-mef Roux J-pyrrolidone solution was added dropwise into the flux of the le and N-Metelucorpyrrolidone solution, and the amine terminal was kept in a flux state for 6 hours while expelling the generated water from the system. A group-containing imide polymer was obtained. 30X to total amine amount
/ 0 (eq, mot/f), Tm: 1757
"" [Imide polymer: Engineering 0-D] 3.3'-diaminodiphenylsulfone o, oθg/
mate and BTDA O,00klImole to 0
An imide polymer containing an amine end group was obtained in the same manner as in Example 1-0. 6s X/o (eq-m
at/? ), Tm co 6 SC to obtain the dark acid chloride of trimellitic anhydride.

Total amine amount 3. zaX/o-” (eq4mot/7
), Tm CoSOC [GA-/] / into the fourth flask, metatoluidine 107.2f (
/mote) and β-methylepichlorohydrin J/
Hydroxide IJ15 to L6f (+moze) (3 times the equivalent amount)
- Taeumha/9g? (θ, θz mode), ethanol, θ0txl, water, and 2 oml were added, and the mixture was reacted for g hours at 60C under a nitrogen atmosphere. Excess β-methylepichlorohydrin was then removed by vacuum distillation.

Next, after adding 5θOml of toluene, a 5θ-containing sodium hydroxide aqueous solution/tlIt<15 times the equivalent amount> was added dropwise using a dropping funnel, and kept at 6sC for 3 hours.
7 t (j m0t) <3.3 times the equivalent weight>.

Add ethanol/00ynl and lithium hydroxide-hydrate dissolved in water, 101ml.

The reaction was carried out at 60C under nitrogen atmosphere for 6 hours. After that, most of the excess β-methylebichlorohydrino-16-dolino was removed by distillation under reduced pressure, and then toluene 'l 00 Il! Add 50% hydroxide) IJium aqueous solution t, y pr
f (equivalent to /S times) was added dropwise over a period of 7 hours.The system was then kept at t,oC for 2 hours.Approximately twice the amount of water was added to the reaction product and washed several times with water. The layers were separated. The liquid product was obtained by vacuum distillation at 100 C1/θtmHy. The epoxy equivalent of this compound was Fi/
, 2 / (t/eq, ).

[GA-,7) p,lI'-diaminodiphenylmethane 1001(o,
r/mote), β-methylepichlorohydrin 6
Saved time. Thereafter, excess β-methylepichlorohydrin was completely removed by vacuum distillation to obtain a reddish-brown viscous liquid.

The epoxy equivalent of this compound is i! rg(y7θq).

Comparative example of preparation of cured product - / m-aminophenol triglycidyl type epoxy (trade name: Sumitomo Chemical Co., Ltd., EjLM -/Co0) C epoxy equivalent / 10 ~ / λ! ry/θq]/ 00 t 41,4”-diaminodiphenylmethane (DDM) l
Heat and mix I3 f in a mold/! rOC//hour ten/
gOC/! A cured product was obtained by curing for r hours. Vicat softening point temperature [TB] of this cured product.

Basic fiber (trade name: Nikurashisha, Trading Card T-aoo) was impregnated with a carbon fiber content of 0 volqA and dried, and then cured using a mold heating press at 77θC/, for 2 hours -〇〇''Q// hours, and cured. The thermal decomposition onset temperature of the cured product on the glass plate was measured by TGA, and the T8 of the composite cured product was measured.

Comparative Example-3 FILM-113'l/Of and amine end group-containing imide polymer (Process 0-A) J 2. ! ; f to 'I
g, gr (7) Dissolve in N,N-dimethylformide and adjust the face. TGA and 'rs were measured for the cured product which was cured at 60°C for 73 hours and 1200°C for 17 hours in the same manner as in Comparative Example C.

Example-/ Diβ-methylglycidyl ester of meta-toluidine Triβ-methylglycidyl type epoxy of p-aminophenol (GA-, 2 synthetic product) Sv Toimi)”fr polymer I O-B ) :l O, A face was prepared by dissolving 4W in 3T, lIf of N,N-dimethylformamide.A cured product was prepared under the same conditions as in the following examples and TG.
A, 'rs was measured.

Example-3 Tetraβ-methylglycidyl type epoxy (GA-3 synthetic product) of Ge, Ri'-diaminodiphenylmethane and imide polymer (0-A) A face was prepared by dissolving it in N,N-dimethylformamide. A cured product was produced and evaluated under the same conditions as in Example-7.

Example-DaGA-j synthetic product 3f and Indian polymer (process 0-B)/1
．． The mixture was dissolved in 3/1 part of N,N-dimethylformamide to prepare a face. The following Example - 5 tons of GA-j synthetic product and imide polymer (0-D) were mixed. 6
．． A cured product prepared by dissolving 3f in N,N-dimethylformamide and producing it under the same conditions as in Example was evaluated.

Example-7 GA-,3 synthetic product S2 and amide-imide polymer (Engineering○-E
) t, 3 tf; 720 t (DN, N-cy'f was dissolved in formamide to prepare a face.The following examples-
A cured product was produced under the same conditions as No. 7 and evaluated as I-.

Data for Comparative Examples/~3 and Examples/~7 are shown in Table-7.

Also, Comparative Example 3 and Example 3. ! , 6 thermal decomposition comparison results (Hθating Rate/ j
C/rmyr, ai, r! The data on the thermobalance at rOynl/min) are shown in FIG.

23- Regarding B, heating rate 73C/min, evening θme 1 minute Applicant Hirobe Yoda, Director of the Agency of Industrial Science and Technology 24-

Claims (1)

[Claims] (1) General formula (I) (In the formula, Ar is a covalent aromatic organic group, Ar' is a divalent aromatic organic group, and each of the carbonyl groups is directly bonded to a different carbon atom. , and each pair of carbonyl groups is A
Ar" is a trivalent aromatic organic group that is bonded to adjacent carbon atoms in the r' group, each of the three carbonyl groups is directly bonded to another carbon atom, and the pair of carbonyl groups is an Ar" group. and n, m is O or a positive integer, m + n)
It is 0. ) and an aromatic amine epoxy resin containing a β-alkylglycidyl group.