JPS61148225A - Curable composition - Google Patents

Abstract

PURPOSE:A quick-curing epoxy resin composition, containing a reactive silicon functional group-containing polyether, epoxy compound, curing catalyst and curing agent in a specific proportion, having improved impact resistance, and useful for molding and processing. CONSTITUTION:A curable composition containing (A) a polyether containing at least one reactive silicon functional group, preferably alkoxysilyl group in one molecule, (B) an epoxy compound having >one epoxy groups in one molecule, preferably 4,4'-dioxydiphenyl-2,2'-propane glycidyl polyether, (C) a polyether curing catalyst, e.g. tetrabutyl titanate, and (D) an epoxy curing agent, preferably an aliphatic amine such as isophoronediamine, as essential components at 2.5/98.5-50/50 weight ratio between the components (A) and (B).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermosetting resin composition, and particularly to an epoxy resin composition for molding that has excellent impact resistance.

(Prior Art and Problems) Epoxy resins have been widely used in the fields of various electrical parts and matrix resins for reinforced plastics because of their excellent heat resistance, electrical properties, and adhesive properties. The epoxy resins used are generally bispheno-7L/A diglycidi V ether type and phenol novolac type, but a major drawback of epoxy resins is poor impact resistance. Furthermore, in automobile parts such as various electrical parts and structural members around heaters, it is desired that they have excellent impact resistance as well as excellent heat resistance, electrical properties, and adhesive properties.

(Means for Solving the Problems) The present inventors have achieved the present invention as a result of intensive research into epoxy resin compositions for molding that have excellent impact resistance and are quick-curing. That is, the present invention comprises: (a) polyethers containing at least one reactive silicone functional group in one molecule; (b) epoxy compounds having an average of more than one epoxy group per molecule; (c ) a polyether curing catalyst, and (6) an epoxy curing agent as essential components, and a core (
Weight ratio of component a)/component (b) is 2.5/98.5 to 5
0150, and particularly relates to an epoxy resin composition for molding.

Polyethers having at least one reactive silicone functional group in the molecule, which are used as component (a) in the present invention, are, for example, Japanese Patent Publications No. 45-"r6'519, No. 46-12154, No. 49- No. 32673, JP-A-6
No. 0-156599, No. 51-735/) IJi3-No. 54-6096, No. 55-13767-F15-
No. 13768, No. 55-82123, No. 55-123
6207°, No. 55-125121, No. 55-131
No. 021, No. 55-131022, No. 55-1351
This polyether is disclosed in publications such as No. 35 and No. 55-137129. The reactive silicon functional group referred to here refers to a group that condenses and reacts with moisture or additives, such as a hydrolyzable group bonded to a silicon atom or a silanol group, and is typically represented by the general formula (1) (formula Among them, B11j-order prime number 1 to 20 substituted or unsubstituted monovalent hydrocarbon group or triorganosiloxy group,
hydroxyl group or a different or similar hydrolyzable group,
b i/'i0.1.2 represents an integer of 3, 0 represents an integer of 0, 1 or 2, m represents an integer of 0 to 18).

A polyether having a reactive silicon functional group such as (3) % formula % (3) -RNHC- or 10- (R is the same or different type of divalent hydrocarbon group having 1 to 20 carbon atoms), Br hydrogen atom or a substituted group having 1 to 2 carbon atoms A polyether V having an olefin group represented by an unsubstituted monovalent organic group, & is an integer of 0''!1 is combined with platinum black, chloroplatinic acid, a platinum alcohol compound, or a platinum olefin complex. It can be produced by addition reaction using platinum compounds such as platinum, platinum aldehyde complex, platinum ketone complex, etc. as a catalyst.

As a method for producing a polyether having a reactive silicone functional group other than the above, (1) a hydroxyl group-terminated polyether is reacted with a polyisocyanate compound such as toluene diisocyanate to form isocyanate group-terminated polyether V; In the formula (4) % formula % (wherein Y is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a capto group and an amino group (primary or secondary), d is 0.1 or A method of reacting the Y group of a silicon compound represented by an integer of 2, R1, a hill, and X the same as above), (b) with an olefin group of a polyether having an olefin group represented by the above general formula (3). , a method of addition-reacting a mercapto group of a silicon compound represented by the general formula (4) in which Y is a merkabuto group, and 011) a method of adding a mercapto group of a silicon compound represented by the general formula (4) in which Y is a mercapto group, and a method of adding a mercapto group of a hydroxyl group-terminated polyether V to a hydroxyl group of the general formula % formula % (1 (in the formula, E' , R, X-d (same as above) may be specifically mentioned, but the present invention is not limited to these methods.

BI in the general formula (2) is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, and specific examples include alkyl groups such as methyl and ethyl; cycloV-kyl groups such as cyclohexyl; and aryl V groups such as l-phenyl groups; aralkyl groups such as benzyl groups, and the like.

Furthermore, Bl may be a trio V ganosiloxane group represented by the general formula % (representing the same or different monovalent hydrocarbon groups having 1 to 20 carbon atoms in Hz), or the general formula (2) or a silanol group or a different or the same type of hydrolyzable group, specific examples of which include, for example, a halogen group,
hydride group, alkoxy group, aminooxy group, ketoximate group, amino group, amide group, aminooxy group,
Examples include mercapto group and alkenyloxy group.

Specific examples of the hydrogenated silicon compound represented by the general formula (2) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane, MethiV dimethoxysilane, phenyldimethoxysilane, 1,3,3°5,5.7
．． 7. -Alkoxysilanes such as heptamethyl-1,1-dimethoxytetrasiloxane; Acyloxysilanes such as methyldiacetoxysilane, trimethylsiloxy, 1methylacetoxysilane, bis(dimethylketoximate) methylsilane, bis(cyclohexylketoximate) Ketoximate silanes such as methylsilane, bis(diethylketoximate)trimethylsiloxysilane, hydrosilanes such as dimethylsilane, trimethylsiloxymethylsilane, and 1,1-dimethy7L/-2,2-dimethyldisiloxane; Examples include (isopropenyloxy)silane and alkenyloxylyranes, but are not limited to these.

In the method of reacting the hydrogenated silicon compound represented by the general formula (2) with the olefin group-containing polyate V represented by the general formula (3), after reacting them, some or all of the The groups represented can be further converted into other hydrolyzable groups or hydroxy V groups. For example, when the group represented by X is a halogen group or a hydride group, it is preferable to use it after converting it into an alkoxy group, an aminooxy group, an aminooxy group, an alkenyloxy group, a hydroxyl group, or the like. In general formula (3), B is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom. , z are divalent organic groups having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, preferably -ROR-1, and methylene group is particularly preferred. A specific method for producing Boriethe V having an olefin group represented by the general formula (3) is the method disclosed in JP-A-54-6097, or the method in which an epoxy compound such as ethylene oxide or propylene oxide is polymerized. Another example is a method in which an olefin group-containing epoxy compound such as allyl glycidyl ether is added and copolymerized to introduce an olefin group into the side chain.

The main chain of the polyether used in the present invention is essentially a divalent organic group represented by the general formula %C in which R3 is a divalent organic group, most of which is a hydrocarbon group having 1 to 4 carbon atoms. It is preferable to have a repeating unit shown in (most preferred). Specific examples of Bl include -0H, -1-CTI, OH, -1-c
TlcTl, -0HOH-1-0-OH, -10
H.

-OHt O'H10HICJh- and the like.

It is preferable that the main chain of the polyether is composed of only one type of repeating unit, and it is preferable that the main chain of the polyether is composed of only one type of repeating unit.

However, especially as R2, -CjHOHy
- is preferred. The molecular weight of the polyether is 500
-30000 is preferred, but 3000-15
000 is more preferable.

Examples of epoxy compounds having an average of more than one epoxy group per molecule used as component (b) in the present invention include polyhydric alcohols with a valence of 2 or more, diphenols, and polyphenols. There are polyglycidyl ethers obtained by epoxidation with μ-hydrin.

The polyphenols used as raw materials include, for example, 4
．． 4'-dioxydiphenyl tv -2,2'-propane (bisphenol A), 4,4'-dioxydiphenylmethane (hisphenol?), 4,4'-dioquine diphenyl sulfone (bispheno-VS), resorcinol, hyrocatechol , resol or novolak-type phenol-formaldehyde condensates. Examples of polyhydric alcohols include diethylene glyco-v1 dipropylene glycol, glycerin, trimethylolpropane, and pentaerythritol. In addition to these polyepoxy compounds, diglycidyl esters of aromatic or aliphatic cicabolic acids,
Examples evaphthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester; cycloaliphatic polyepoxy compounds such as vinylcyclohexene diepoxide, dicyclobentadiene diepoxide, 13.4-EboxyV-6-methylcyclohexylmethyl, 3 , 4-epoxy-6-methyV cyclohexane carbonate, etc. can also be used.

If desired, it may also be substituted with non-interfering groups such as halogen atoms, hydroxyl groups, and ether groups.

The polyether v curing catalyst used as component (c) in the present invention includes titanate esters such as tetrabutyl titanate and tetrapropyl titanate; diptyltin dilaurate, diptyltin maleate, dibutyltin diacetate, silver octate, Organotin compounds such as silver naphthenate, lead octylate; butylamine, octylamine, diptylamine, monoethanolamine, jetanolamine, triethanolocyamine, diethylenetriamine,
Triethylenediamine, oleylamine, octylamine, cyclohexylamine, benzicyamine, diethylaminopropylamine, xylylenecyamine, triethylenediamine, guanidine, diphenylquanidine, 2
,4. /)-)Amine compounds such as lis(dimethylaminomethyl)phenol, moV-V, N-methylmorpholine, 1,3-diazabicyclo(5,4,6)undecene-7 (DBU), or their carboxylic acids, etc. A low molecular weight polyamide resin produced by an excess of polyamine and a polybasic acid. A reaction product of an excess of polyamine and an epoxy compound; a silane coupling agent having an amino group;
For example, γ-aminopropyltrimethoxine, N-
One or two known silanol condensation catalysts such as (β-aminoethyl)aminopropylmethyldimethoxysilane
More than one species can be used.

As the epoxy curing agent used as component (a) in the present invention, various conventionally known epoxy curing agents can be used. For example, phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, dodecylsuccinic anhydride, methylnadic anhydride, chlorendic anhydride, penzophenonetethocarboxylic anhydride , acid anhydrides such as butanetetracarboxylic anhydride; ethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, N-aminoethylpibefudine, bis(4
- Amine compounds such as (amino-3-methylcyclohexyl) methane, metaxylylene amine, menthanediamine, isophorone diamine, etc. - Modified aliphatic polyamines such as diethylenetriamine adduct, cyanoethylated polyamine; phenol, bisphenol A, bispheno-y F , tetrabromobisphenol A1
Examples include phenolic compounds such as cresol; xylene resin, etc. In the present invention, it is particularly preferable to use aliphatic polyamines among these.The amount of curing agent used is determined by the ratio of the number of epoxy groups in the commonly used polyglycidyl V compound to the number of functional groups in this curing agent. Although it is stoichiometrically determined by, it is not necessarily limited to this.

The ratio of component (a) and component (b) in the present invention is determined based on the mechanical strength and heat resistance of the molded product obtained.
) component/(b) component weight ratio 2.5/98.5-501
It is preferable to set it in the range of 50.

To the curable composition of the present invention, a modifier such as a coupling agent, a viscosity modifier, etc. may be added in an appropriate amount within a range that does not impede the object of the present invention.

Further, reinforcing materials such as glass fiber, organic fiber, carbon fiber, etc. may be added.

The compositions of the invention can be used in coating and impregnating compositions and also in reinforced composite products such as laminates, filament finding, and botting. In particular, the composition of the invention is suitable for use in reaction injection molding (R-M).

The curing reaction of the composition of the present invention is usually carried out at a temperature of 80 to 150°C.
Heat for about 1 to 30 minutes to gel, then reduce the temperature to 13
This is carried out by heating at 0 to 180°C for 1 to 5 hours.

(Examples) Next, the present invention will be explained by examples, but the present invention is not limited only to these examples. In the following examples, parts are parts by weight.

Examples 1 to 3 A mixed solution having the composition shown in Table 1 was preheated to 140"C. The dimensions of the cavity were 300m+, 200I wide, and 3H high.
The mold was busy injected. Gelation time was approximately 3 minutes. After leaving the mold as it was for 15 minutes, the cured product was removed from the mold and subjected to a post-curing reaction for 1 hour in an open environment at 160°C.
A cured product shown in Table 1 was obtained.

The abbreviations in Table 1 are as follows.

MS: 80% of all terminals are reactive silicon functional lds groups ((cHsO) 81 CHx OIh OHt O
Silyl group-terminated polypropylene oxide with an average molecular weight of about 8,000 gp: t'suphenol A diglycidyl ether (manufactured by Yuka Epoxy ■, trade name Ko Pico-82B) Engineering PD: Isophoronediamine DETL Nidibutyltin dilaurate comparative example 1 100 parts of 1 vol. of bisphenol A diglycidyl ether and 22 parts of isophorone diamine were mixed, and a cured product shown in Table 1 was obtained in the same manner as in Example 1.

In this case, the Izod impact strength was inferior to Examples 1-3.

Claims (1)

[Claims] 1. (a) a polyether containing at least one reactive silicone functional group in one molecule; (b) an epoxy compound having on average more than one epoxy group per molecule; , containing (c) a polyether curing catalyst and (d) an epoxy curing agent as essential components, and having a weight ratio of component (a)/component (b) of 2.5/98.5 to 50/50. A curable composition. 2. The composition according to claim 1, wherein the reactive silicone functional group of component (a) is an alkoxysilyl group. 3. The composition according to claim 1, wherein the epoxy compound of component (b) is a glycidyl polyether of polyhydric phenol. 4. Polyhydric phenol is 4,4'-dioxydiphenyl-
A composition according to claim 3, which is 2,2'-propane. 5. The composition according to claim 1, wherein the curing agent of component (d) is an aliphatic polyamine.