JP2911225B2 - Imide compound, curable composition containing the same, and cured product obtained therefrom - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel imide compound, a curable composition containing the imide compound, and a cured product obtained therefrom. More specifically, an imide compound which is a liquid or a solid having a low melting point at room temperature, and gives a cured product having excellent heat resistance, chemical resistance and mechanical properties after curing, a curable composition containing them, and a curable composition containing them It relates to the cured product obtained from

[0002]

2. Description of the Related Art Conventionally, various types of room temperature curable resin compositions have been developed. However, most curable resin compositions which give cured products having excellent heat resistance, chemical resistance and mechanical properties after curing have been developed. Not developed.

As a room temperature curable resin composition, a composition containing a silyl ether group-terminated polyether has been disclosed (JP-A-52-73998). The cured product obtained from this composition is rubbery at room temperature and has excellent mechanical properties such as elongation, especially at low temperatures, but at temperatures above 100 ° C the mechanical strength is greatly reduced. , Can not be used effectively at such high temperatures. Further, this cured product has a fatal disadvantage that it is inferior in chemical resistance, particularly acid resistance because the main chain is polyether.

Further, a room temperature curable resin composition having a main chain of polyester has been disclosed (Japanese Patent Publication No. 49-32673). In general, polyester is superior in heat resistance and acid resistance as compared with polyether, but the main chain is still insufficient in heat resistance and chemical resistance of a cured product obtained from a room temperature curable resin composition composed of polyester. I haven't been satisfied yet.

[0005]

According to the present invention, the heat resistance and chemical resistance of the cured product obtained from the above-mentioned conventional room temperature curable resin composition are not yet sufficient, and a satisfactory product has not yet been obtained. This was done to solve the problem.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a compound having an imide skeleton directly linked to an aliphatic cyclic structure and a reactive silicon group in the same molecule is obtained. , Found to be a liquid or a solid having a low melting point at room temperature, and further found that the use of the compound makes it easy to prepare a cured product and gives a cured product having excellent heat resistance and chemical resistance after curing. Thus, the present invention has been completed.

The present invention provides a compound represented by the general formula (I):

[0008]

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(Wherein R ⁰ represents two aromatic diamines
Divalent organic group having 6 to 30 carbon atoms excluding amino group or
Two amino groups removed from Loxanediamine

[0010]

[0011] The divalent organic group, R ¹ is the general formula:

Embedded image (Wherein Y is a general formula (III):

Embedded image (Wherein, R ⁴ is an alkyl group having 1 to 20 carbon atoms,
20 aryl groups, aralkyl groups having 7 to 20 carbon atoms or one
General formula:

Embedded image (Wherein, R ⁵ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms)
And three R ^{5 s} may be the same or different
X) is an alkoxy group or
Represents an acyloxy group, a is 1, 2 or 3;
When two or more R ⁴ or X are present, they are the same and
Which may be different)
Represents a divalent organic group represented in the two R ¹ may be the same, imide compounds represented by different may be), the general formula (I) imide compound and a silanol condensation catalyst represented by And a curable composition containing the imide compound represented by the general formula (I) or the imide compound and a silanol condensation catalyst, cured by moisture and / or heat. Cured product.

[0012]

Action and Examples The imide compound of the present invention has the general formula
(I):

[0013]

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An imide compound represented by the formula:

In the general formula (I), R ⁰ is an aromatic diamine
Dividing the two amino groups from down two divalent organic group or a siloxane diamine having 6 to 30 carbon atoms excluding amino group
Was

[0016]

[0017] a divalent organic group, especially aromatic di
2 to 6 carbon atoms , excluding two amino groups from the amine
A divalent group comprising a divalent aromatic group or an aromatic ring bonded through a divalent group is preferable in that a cured product having excellent heat resistance is obtained after curing, and specific examples of particularly preferable groups are particularly preferred. Are 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3 '
-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,3'- Diaminobenzophenone, bis {4- (4-aminophenoxy) phenyl} sulfone, bis {4- (3-aminophenoxy) phenyl} sulfone, bis {4- (2-aminophenoxy) phenyl} sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, bis ｛4-
(4-aminophenoxy) phenyl} ether, 4,4'-
Diaminodiphenylmethane, bis (3-ethyl-4-aminophenyl) methane, bis (3-methyl-4-aminophenyl) methane, bis (3-chloro-4-aminophenyl) methane, 4,4′-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, 3,3'-dimethoxy-4,4'-
Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2 ', 5,5'-tetrachloro-4,4' -Diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,4-diaminotoluene, 1,3-diaminobenzene, 1 , 4-Diaminobenzene, 2,2'-bis {4- (4-aminophenoxy) phenyl} propane, 2,2'-bis {4-
(4-aminophenoxy) phenyl @ hexafluoropropane, 2,2'-bis (4-aminophenyl) propane,
2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-hydroxy-4-aminophenyl)
Propane, 2,2'-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 9,9'-bis (4-aminophenyl) -10-hydroanthracene, orthotrizine sulfone, 1,2-xylylenediamine Aromatic diamines such as 1,3-xylylenediamine and 1,4-xylylenediamine; 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,5-bis (3-aminopropyl) hexa methyl birds siloxanyl down

[0018]

[0019] The What siloxane diamines such as residues obtained by removing an amino group and the like, may be used as singly or two or more thereof.

In the general formula (I), R ¹ is a general formula:

Embedded image (Where Y is a general formula (III):

Embedded image (Wherein, R ⁴ is an alkyl group having 1 to 20 carbon atoms,
20 aryl groups, aralkyl groups having 7 to 20 carbon atoms or one
General formula:

Embedded image (Wherein, R ⁵ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms)
And three R ^{5 s} may be the same or different
X) is an alkoxy group or
Represents an acyloxy group, a is 1, 2 or 3;
When two or more R ⁴ or X are present, they are the same and
Which may be different)
A divalent organic group represented by the general formula (III) , in particular, directly on a carbon atom forming a ring
And a reactive silicon group ) are preferred.

[0021]

[0022]

[0023]

[0024]

[0025] The R ⁴ includes, as described above, 1 or 2 carbon atoms
0, preferably an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 15 carbon atoms .

[0026]

[0027]

Specific examples of R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Hexyl, heptyl, octyl, nonyl, decyl, dodecyl, isopropyl, isobutyl, t-
Butyl group, alkyl group such as isooctyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, cycloalkyl group such as methylcyclohexyl group,
Benzyl group, phenethyl group, aralkyl group such as cumyl group, trimethylsiloxy group, triethylsiloxy group,
Examples include a t-butyldimethylsiloxy group, a dimethylphenylsiloxy group, a methyldiphenylsiloxy group, and a triphenylsiloxy group.

Specific examples of R ⁵ in the above general formula include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl Group, isobutyl group, isooctyl group, phenyl group and the like.

[0030] Further, X in the general formula (III), an alkoxy group, an acyloxy group are preferable, reactive alkoxy group from the viewpoint of proceeds under mild conditions, especially preferred.

A in the general formula (III) is 1, 2 or 3. That is, the group represented by X can be bonded to one silicon atom in the range of 1 to 3 groups. When a is 2 or 3, the groups represented by X may be the same,
It may be different.

Specific examples of the imide compound of the present invention are shown below, but the imide compound of the present invention is not limited to these specific examples.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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The method for producing the imide compound of the present invention is not particularly limited, and includes, for example, several methods combining known techniques. Among them, first the general formula
(V):

[0039]

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Wherein R ⁰ is the same as above, and R ⁶ is a group represented by the formula :

[0041]

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At least one group selected from the divalent organic groups represented by the following formula) can be used to synthesize an imide compound containing two cyclic olefins in the same molecule represented by the formula: The method of introducing a group is particularly preferable in terms of workability, yield, and the like.

As a method for producing the imide compound containing two cyclic olefins in the same molecule, the following method is known as a known technique. That is, a diamine component and a cyclic olefin-containing anhydride are reacted in an organic polar solvent to obtain an amic acid solution, and then heated to thermally imidize the diamine component and a cyclic olefin-containing acid. A method of reacting the anhydride with an anhydride in an organic polar solvent to obtain a solution of an amic acid, and then reacting the solution with a dehydrating agent such as acetic anhydride to chemically imidize the diamine component and the cyclic olefin-containing anhydride. Is reacted in an organic polar solvent to obtain a solution of amic acid, and then the solution is contacted with water, a poor solvent for amic acid such as hydrocarbon to precipitate amic acid as a precipitate, which is heated, Specific examples include a method in which a diisocyanate component and a cyclic olefin-containing acid anhydride are reacted in an organic polar solvent to directly obtain an imide compound.

By any of these methods, an imide compound containing two cyclic olefins in the same molecule can be produced and is not particularly limited, but the production apparatus and the production process are simpler or easier. Due to the fact that it is easy to obtain the raw materials used,
That is, a diamine component and a cyclic olefin-containing acid anhydride in an organic polar solvent, for example, dimethyl sulfoxide, sulfoxide solvents such as diethyl sulfoxide,
Formamide solvents such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, acetamido solvents such as N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-acetyl- Pyrrolidone solvents such as 2-pyrrolidone and N-vinyl-2-pyrrolidone,
Phenol, o-cresol, m-cresol, p-cresol, xylenol, halogenated phenol, phenolic solvents such as catechol, or pyridine, hexamethylphosphoramide, γ-butyrolactone, and a mixture of two or more of these, A method is preferred in which the reaction is carried out at a temperature of 80 ° C. or less to obtain a solution of amic acid, which is then heated to 100 to 250 ° C. to obtain a compound represented by the general formula (V).

The introduction of the reactive silicon group into the cyclic olefin-containing imide compound may be carried out by a known method, and is not subject to any restrictions. As a specific example, there is a method of reacting hydrosilane having a reactive group to perform hydrosilylation. Hydrosilane has the general formula (VI):

[0046]

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(Wherein R ⁴ , X and a are the same as described above, and when two or more X and R ⁴ are present, they may be the same or different) It is.

[0048] Introduction of the reactive silicon group into the cyclic olefin-containing imide compound, for example H ₂ PtCl ₆ · 6H ₂ O
, Pt metal, RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al _{2
O 3, RuCl 3, IrCl 3} , FeCl 3, AlCl 3, PdCl 2 · 2H 2 O
, NiCl ₂ , a compound such as TiCl ₄ as a catalyst,
It can be achieved by performing a hydrosilylation reaction.

The hydrosilylation reaction is generally carried out at 0 to 150 ° C.
If necessary, hexane, heptane, benzene, toluene, hydrocarbon solvents such as xylene, methanol, ethanol, propanol, ethylene glycol, alcohol solvents such as 1,4-butanediol, Ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and anisole; and ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate, and ethyl benzoate A suitable organic solvent such as a solvent or a mixture of two or more halogenated hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride and chlorobenzene may be used.

The imide compound of the present invention is a liquid at room temperature or shows a melting point of 250 ° C. or less, and a hydrocarbon solvent such as hexane, heptane, benzene, toluene and xylene, methanol, ethanol, propanol, ethylene glycol, 1,4 -Alcohol solvents such as butanediol, diethyl ether, tetrahydrofuran, 1,4-dioxane,
Ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and anisole; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate, and ethyl benzoate; methylene chloride, chloroform, ethylene chloride, and chlorobenzene And can be cured at a temperature of 250 ° C. or less, preferably 200 ° C. or less, even in the absence of a catalyst, while being soluble in halogenated hydrocarbon solvents. When a condensation catalyst is used, the composition cures at a temperature as low as 0 to 200 ° C, preferably 0 to 100 ° C. The resins cured by these two different methods have essentially the same properties,
All have excellent heat resistance, chemical resistance, and mechanical properties.

The composition of the present invention is a composition comprising one or more of the imide compounds represented by the general formula (I) and one or more of the silanol condensation catalyst.

Specific examples of the silanol condensation catalyst in the composition of the present invention include, for example, titanates such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, octylic acid, tin stannaphthenate Reaction products of dibutyltin oxide and phthalic acid esters; dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetra Chelating compounds such as acetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octy Amine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6 -Tris (dimethylaminomethyl)
Phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0
) Amine compounds such as undecene-7 (DBU) or salts thereof with carboxylic acids and the like; low molecular weight polyamide resins obtained from excess polyamine and polybasic acid; reaction products of excess polyamine and epoxy compound; Known silane coupling agents having an amino group, such as silanol condensation catalysts such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane, as well as other acidic catalysts and basic catalysts And a silanol condensation catalyst. These catalysts may be used alone or in combination of two or more.

When a silanol condensation catalyst is used, the amount used is preferably 0.01 to 20 parts with respect to 100 parts (parts by weight, hereinafter the same) of the imide compound represented by the general formula (I), and 0.1 to 20 parts.
~ 10 parts is more preferred. If the amount of the silanol condensation catalyst used is too small, the curing speed will not be too high, and the effect of using the catalyst will not be sufficiently obtained. On the other hand, if the amount of the silanol condensation catalyst used is too large, local heat generation or foaming occurs during curing, making it difficult to obtain a good cured product.

When the imide compound is a liquid, it is possible to prepare a composition by directly mixing the two components of the imide compound represented by the general formula (I) and the silanol condensation catalyst.

When the imide compound is a solid, the imide compound is converted into an appropriate organic solvent, for example, a hydrocarbon solvent such as hexane, heptane, benzene, toluene, xylene, methanol, ethanol, propanol, ethylene glycol, Alcohol solvents such as, 4-butanediol, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ether solvents such as anisole, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, It is dissolved in an ester solvent such as methyl benzoate and ethyl benzoate, or a single or a mixture of two or more halogenated hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride and chlorobenzene. By adding Nord condensation catalyst, it is possible to prepare a composition.

The composition of the present invention may further contain, if necessary, an adhesion improver, a physical property modifier, a storage stability improver, a plasticizer, a filler, an antioxidant, an ultraviolet absorber, and a metal deactivator. Various additives such as an ozone deterioration inhibitor, a light stabilizer, an amine radical chain inhibitor, a phosphorus peroxide decomposer, a lubricant, a pigment, and a foaming agent may be appropriately compounded. The total amount of the additives is not particularly limited as long as it does not significantly reduce various properties of the cured product, but more preferably the imide compound
1 to 300 parts for 100 parts.

To cure the imide compound of the present invention,
The imide compound has a melting point of 250 ° C. or less, preferably
It only needs to be treated in a temperature range of 200 ° C. or less for 5 minutes to 24 hours. To cure the composition of the present invention containing a silanol condensation catalyst, the temperature is preferably from 0 to 200 ° C, preferably from 0 to 100 ° C.
It only needs to be treated in a temperature range of ° C. for 1 minute to 24 hours. If the treatment temperature is too high, local heat generation or foaming occurs during curing, and it becomes difficult to obtain a good cured product.

When the composition of the present invention contains an organic solvent, the composition is heated to a temperature at which the organic solvent used can be volatilized (may be lower than the boiling point) and / or
It is preferable to cure the organic solvent by evaporating it by treating it under reduced pressure at a temperature not higher than the boiling point of the organic solvent used.

The cured product of the present invention obtained by curing the imide compound and the curable composition of the present invention has excellent heat resistance, chemical resistance, and mechanical properties, and has various uses such as a resin modifier. And a heat-resistant coating material.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to only these Examples.

Example 1 2,3-Dicarboxyl-bicyclo [2.2.1] under a stream of nitrogen
32.8 g (0.20 mol) of hepta-5-ene anhydride was dissolved in 200 ml of N, N-dimethylacetamide (hereinafter referred to as DMAc). At room temperature, 40.0 g (0.10 mol) of 4,4'-diaminodiphenyl ether was added to 200 ml of DMAc at room temperature.
Was gradually added over about 30 minutes. After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution. Subsequently, the obtained amic acid solution was heated to reflux, and further heated and stirred for 3 hours. After allowing to cool, the reaction solution was poured into a large amount of methanol to precipitate the product, followed by filtration. The obtained precipitate was washed with methanol and dried under reduced pressure at room temperature for several hours to obtain an imide compound.

[0062] The obtained imide compounds 10g was dissolved in chlorobenzene one liter it 1g of H ₂ PtCl ₆ · 6H
1.02 ml of a solution of ₂ O in 10 ml of ethanol was added. At room temperature, 43.1 g of methyldimethoxysilane was added by a dropping funnel and reacted at 100 ° C. for 30 hours. After the reaction, the reaction solution was poured into methanol, reprecipitated, filtered, washed with methanol, and dried under reduced pressure at room temperature for several hours to obtain an imide having a target reactive silicon group represented by the following formula (VII). 11.5 g of compound (VII) was obtained.

[0063]

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Melting point: 180 ° C. ¹ H NMR (CDCl ₃ ) δ: 0.20 (s, 6H, Si
CH ₃ ), 1.47, 1.65 (dd, 4H, CCH ₂ C), 1.
69-1.95 (m, 6H, CCH ₂ CHSi), 2.88 (s,
2H, C H CHSi), 3.25 (s, 2H, C H CH 2 C
HSi), 3.50 (s, 12H, Si (OCH ₃ ) ₂ ), 3.
55 (d, 4H, CHCO), 7.14-7.24 (m, 8H, C
₆ H _4).

Example 2 To 5 g of the imide compound (VII) obtained in Example 1 was added 20 g of chloroform to prepare a chloroform solution of the imide compound (VI), and 0.15 g of tin octylate was used as a curing catalyst.
And 0.038 g of laurylamine were blended to obtain a thermosetting composition. Storing the composition at 50 ° C. and 60% relative humidity for 4 days,
Thereafter, curing was further performed at 250 ° C. for 5 hours to prepare a cured product.

The obtained cured product was subjected to TGA measurement using a differential thermal balance TG-DTA manufactured by Rigaku Corporation. Table 1 shows the obtained 5% or 10% weight loss temperature. Table 2 shows the appearance of the cured product after immersion in N, N-dimethylformamide and 10% hydrochloric acid for 10 days.

Example 3 5 g of the imide compound (VII) obtained in Example 1 was stored in a perfect oven maintained at 180 ° C. for 6 hours without adding a condensation catalyst. The solid obtained by this treatment was insoluble in chloroform.

The obtained cured product was subjected to TGA measurement using a differential thermal balance TG-DTA manufactured by Rigaku Corporation. Table 1 shows the obtained 5% or 10% weight loss temperature. Table 2 shows the appearance of the cured product after immersion in N, N-dimethylformamide and 10% hydrochloric acid for 10 days.

Example 4 2,3-Dicarboxyl-bicyclo [2.2.1] under a stream of nitrogen
32.8 g (0.20 mol) of hepta-5-ene anhydride
Dissolved in 200 ml. Add 4,4 at room temperature to the resulting solution.
´-Diaminodiphenyl sulfone 24.8g (0.10mol)
Was dissolved slowly in 200 ml of DMAc over about 30 minutes. After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution. Subsequently, the same treatment as in Example 1 was performed to obtain an imide compound.

[0070] dissolved the obtained imide compound 10g in chlorobenzene one liter thereto of _{H 2 PtCl 6 · 6H 2 O} 1
0.93 ml of a 0% ethanol solution was added. At room temperature, add 46.6 g of trimethoxysilane through a dropping funnel, and add
For 40 hours. After the reaction, the reaction solution is poured into methanol, reprecipitated, filtered, washed with methanol, and dried under reduced pressure at room temperature for several hours to obtain an imide having a target reactive silicon group represented by the following formula (VIII). Compound (V
III) 10.8 g was obtained.

[0071]

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Example 5 20 g of chloroform was added to 5 g of the imide compound (VIII) obtained in Example 4 to prepare a chloroform solution of the imide compound (VIII), and tin octylate 0.15 was used as a curing catalyst.
g and laurylamine 0.038 g were blended to obtain a thermosetting composition. The composition was stored at 50 ° C. and a relative humidity of 60% for 4 days, and then cured at 250 ° C. for 5 hours to prepare a cured product.

The obtained cured product was subjected to TGA measurement using a differential thermal balance TG-DTA manufactured by Rigaku Corporation. Table 1 shows the obtained 5% or 10% weight loss temperature. Table 2 shows the appearance of the cured product after immersion in N, N-dimethylformamide and 10% hydrochloric acid for 10 days.

Example 6 5 g of the imide compound (VIII) obtained in Example 4 was stored in a perfect oven maintained at 180 ° C. for 6 hours without adding a condensation catalyst. The solid obtained by this treatment was insoluble in chloroform.

The obtained cured product was subjected to TGA measurement using a differential thermal balance TG-DTA manufactured by Rigaku Corporation. Table 1 shows the obtained 5% or 10% weight loss temperature. Table 2 shows the appearance of the cured product after immersion in N, N-dimethylformamide and 10% hydrochloric acid for 10 days.

Example 7 33.2 g (0.20 mol) of 2,3-dicarboxyl-7-oxabicyclo [2.2.1] hept-5-ene anhydride was added to D in a stream of nitrogen.
MAc was dissolved in 200 ml. At room temperature, 10.8 g (0.10 mol) of 4,4'-diaminobenzene was added to DMAc
The solution dissolved in 200 ml was gradually added over about 30 minutes. After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution. Subsequently, the same treatment as in Example 1 was performed to obtain an imide compound.

[0077] dissolved the obtained imide compound 10g in chlorobenzene one liter thereto of _{H 2 PtCl 6 · 6H 2 O} 1
1.24 ml of a 0% ethanol solution was added. At room temperature, 81.2 g of triethoxysilane was added with a dropping funnel, and 100
The reaction was performed at 20 ° C. for 20 hours. After the reaction, the reaction solution is poured into methanol, reprecipitated, filtered, washed with methanol, and dried under reduced pressure at room temperature for several hours to obtain an imide having a target reactive silicon group represented by the following formula (IX). Compound (I
X) I got 12.1g.

[0078]

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Example 8 20 g of chloroform was added to 5 g of the imide compound (IX) obtained in Example 7 to prepare a chloroform solution of the imide compound (IX), and 0.15 g of tin octylate and 0.038 g of laurylamine were used as curing catalysts. g) to give a thermosetting composition. The composition was stored at 50 ° C. and a relative humidity of 60% for 4 days, and then cured at 250 ° C. for 5 hours to prepare a cured product.

The obtained cured product was measured for TGA using a differential thermal balance TG-DTA manufactured by Rigaku Corporation. Table 1 shows the obtained 5% or 10% weight loss temperature. Table 2 shows the appearance of the cured product after immersion in N, N-dimethylformamide and 10% hydrochloric acid for 10 days.

Example 9 1,2,3,6-Tetrahydrophthalic anhydride 30.4 in a stream of nitrogen
g (0.20 mol) was dissolved in 200 ml of DMAc. Add 4,4'-diaminodiphenylmethane at room temperature
A solution of 19.8 g (0.10 mol) dissolved in 200 ml of DMAc was gradually added over about 30 minutes. After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution. Subsequently, the same treatment as in Example 1 was performed to obtain an imide compound.

[0082] dissolved the obtained imide compound 10g in chlorobenzene one liter thereto of _{H 2 PtCl 6 · 6H 2 O} 1
1.10 ml of a 0% ethanol solution was added. At room temperature, 46.9 g of methyldiacetoxysilane was added by a dropping funnel and reacted at 110 ° C. for 30 hours. After the reaction, the reaction solution was poured into methanol, reprecipitated, filtered, washed with methanol, and dried under reduced pressure at room temperature for several hours to obtain the following formula (X)
Thus, 11.8 g of the desired imide compound (X) having a reactive silicon group represented by the formula was obtained.

[0083]

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Example 10 5 g of the imide compound (X) obtained in Example 9 was stored for 6 hours in a perfect oven maintained at 180 ° C. without adding a condensation catalyst. The solid obtained by this treatment was insoluble in chloroform.

The obtained cured product was subjected to TGA measurement using a differential thermal balance TG-DTA manufactured by Rigaku Corporation. Table 1 shows the obtained 5% or 10% weight loss temperature. Table 2 shows the appearance of the cured product after immersion in N, N-dimethylformamide and 10% hydrochloric acid for 10 days.

Example 11 2,3-Dicarboxyl-bicyclo [2.2.1] in a stream of nitrogen
33.2 g (0.20 mol) of hepta-5-ene anhydride in 200 ml of DMAc
Was dissolved. At room temperature, 41.0 g (0.10 mol) of 2,2-bis [4- (aminophenoxy) phenyl] propane was added to DMAc 4
The solution dissolved in 00 ml was slowly added over about 30 minutes.
After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution. Subsequently, the same treatment as in Example 1 was performed to obtain an imide compound.

[0087] dissolved the obtained imide compound 10g in chlorobenzene one liter thereto of _{H 2 PtCl 6 · 6H 2 O} 1
0.93 ml of a 0% ethanol solution was added. At room temperature, 39.5 g of dimethoxymethylsilane was added with a dropping funnel, and 1
The reaction was performed at 00 ° C. for 20 hours. After the reaction, the reaction solution was poured into methanol, reprecipitated, filtered, washed with methanol, and dried at room temperature for several hours to obtain 9.9 g of the desired imide compound having a reactive silicon group (XI).

[0088]

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Example 12 A chloroform solution of an imide compound was prepared by adding 20 g of chloroform to 5 g of the imide compound (XI) obtained in Example 11, and 0.15 g of tin octylate was used as a curing catalyst.
And 0.038 g of laurylamine were blended to obtain a thermosetting composition. Storing the composition at 50 ° C. and 60% relative humidity for 4 days,
Thereafter, curing was further performed at 250 ° C. for 5 hours to produce a cured product.

The obtained cured product was subjected to TGA measurement under a stream of nitrogen using a differential thermal balance TG-DTA manufactured by Rigaku Corporation. Table 1 shows the obtained 5% or 10% weight loss temperature.
Shown in The cured product was N, N-dimethylformamide, 10
Table 2 shows the appearance after immersion in 10% hydrochloric acid for 10 days.

Example 13 2,3-Dicarboxyl-7-oxabicyclo under a stream of nitrogen
[2.2.1] 33.2 g (0.20 mol) of hepta-5-ene anhydride in DMAc
Dissolved in 200 ml. At room temperature, 21.8 g (0.10 mol) of 1,3- (3-diaminopropyl) tetramethyldisiloxane
A solution dissolved in 200 ml of DMAc was gradually added over about 30 minutes. After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution. Subsequently, the same treatment as in Example 1 was performed to obtain an imide compound.

[0092] dissolved the obtained imide compound 10g in chlorobenzene one liter thereto of _{H 2 PtCl 6 · 6H 2 O} 1
1.95 ml of a 0% ethanol solution was added. At room temperature, 41.3 g of dimethoxymethylsilane was added with a dropping funnel.
The reaction was performed at 00 ° C. for 20 hours. After the reaction, the reaction solution was poured into methanol, reprecipitated, filtered, washed with methanol, and dried at room temperature for several hours to obtain 10.9 g of the desired imide compound having a reactive silicon group (XII).

[0093]

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Example 14 To 5 g of the imide compound (XII) obtained in Example 13 was added 20 g of chloroform to prepare a chloroform solution of the imide compound, and tin octylate 0.15 was used as a curing catalyst.
g and laurylamine 0.038 g were blended to obtain a thermosetting composition. Storing the composition at 50 ° C. and 60% relative humidity for 4 days,
Thereafter, curing was further performed at 250 ° C. for 5 hours to produce a cured product.

The obtained cured product was subjected to TGA measurement under a stream of nitrogen using a differential thermal balance TG-DTA manufactured by Rigaku Corporation. Table 1 shows the obtained 5% or 10% weight loss temperature.
Shown in The cured product was N, N-dimethylformamide, 10
Table 2 shows the appearance after immersion in 10% hydrochloric acid for 10 days.

Comparative Example 1 To 100 parts of a polypropylene glycol having a dimethoxymethylsilyl group at both terminals (molecular weight: about 8000), 3 parts of tin octylate and 0.75 part of laurylamine were added and kneaded. After storage for 4 days at 60 ° C. (relative humidity 60%), a rubbery cured product was obtained.

The obtained cured product was subjected to TGA measurement using a differential thermal balance TG-DTA manufactured by Rigaku Corporation. Table 1 shows the obtained 5% or 10% weight loss temperature. Also,
Table 2 shows the appearance after immersing the cured product in N, N-dimethylformamide and 10% hydrochloric acid for 10 days.

Comparative Example 2 Poly (γ-methyl-δ-valerolactone) having dimethoxymethylsilyl groups at both ends instead of polypropylene glycol having dimethoxymethylsilyl groups at both ends of Comparative Example 1 (molecular weight: about 8,000) A rubber-like cured product was obtained in exactly the same manner as in Comparative Example 1 except for using.

The obtained cured product was subjected to TGA measurement using a differential thermal balance TG-DTA manufactured by Rigaku Corporation. Table 1 shows the obtained 5% or 10% weight loss temperature. Also,
Table 2 shows the appearance after immersing the cured product in N, N-dimethylformamide and 10% hydrochloric acid for 10 days.

[0100]

[Table 1]

[0101]

[Table 2]

From Tables 1 and 2, it can be seen that cured products from the imide compounds and compositions of the present invention have excellent heat resistance and chemical resistance.

[0103]

The imide compound of the present invention has a relatively low melting point and is excellent in solubility in organic solvents. The curable composition comprising the imide compound or the imide compound and a silanol condensation catalyst can be easily formed into cured products of various shapes, and the obtained cured product has excellent heat resistance, chemical resistance and mechanical properties. Characteristic.

Continuation of the front page (56) References JP-A-2-77467 (JP, A) JP-A-2-62884 (JP, A) JP-A-60-17321 (JP, A) JP-A-59-131629 (JP) JP-A-50-123665 (JP, A) U.S. Pat. No. 4,656,235 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/18 C08G 77/382 C08G 77/54 C08L 83/14 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (3)

(57) [Claims] [Claim 1] General formula (I): (Wherein R ⁰ is the removal of two amino groups from an aromatic diamine)
There was a divalent organic group or a siloxane Zia having 6 to 30 carbon atoms
R ¹ is a divalent organic group obtained by removing two amino groups from a min.
General formula: (Wherein Y is a general formula (III): (Wherein, R ⁴ is an alkyl group having 1 to 20 carbon atoms,
20 aryl groups, aralkyl groups having 7 to 20 carbon atoms or one
General formula: (Wherein, R ⁵ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms)
And three R ^{5 s} may be the same or different
X) is an alkoxy group or
Represents an acyloxy group, a is 1, 2 or 3;
When two or more R ⁴ or X are present, they are the same and
Which may be different)
In represents a divalent organic group represented by the two R ¹ may be the same, imide compounds represented by may be different). 2. A curable composition comprising the imide compound according to claim 1 and a silanol condensation catalyst. 3. A cured product obtained by curing the imide compound according to claim 1 or the curable composition according to claim 2 with moisture and / or heat.